JP7057823B2 - Continuous fiber reinforced resin molded body and its manufacturing method - Google Patents
Continuous fiber reinforced resin molded body and its manufacturing method Download PDFInfo
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C43/00—Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
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- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
- B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
- B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
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- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/40—Shaping or impregnating by compression not applied
- B29C70/42—Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
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- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29K2101/00—Use of unspecified macromolecular compounds as moulding material
- B29K2101/12—Thermoplastic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
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- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/06—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
- B29K2105/08—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns
- B29K2105/0872—Prepregs
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- B29K2309/00—Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
- B29K2309/08—Glass
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- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/3481—Housings or casings incorporating or embedding electric or electronic elements
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- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
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Description
本発明は、連続繊維強化樹脂成形体、及びその製法に関する。より詳しくは、本発明は、連続強化繊維と合成樹脂との間の極界面における接着力、親和性が高く、該極界面に存在する空隙が少なく、十分な強度を発現することができる連続繊維強化樹脂成形体、連続繊維強化樹脂成形体の損失正接が十分小さく、十分な衝撃吸収を発現することができる連続繊維強化樹脂成形体、連続繊維強化樹脂成形体の貯蔵弾性率が十分大きく、十分な衝撃強度を発現することができる連続繊維強化樹脂成形体、樹脂含浸性が高く、高い強度や剛性を有する連続繊維強化樹脂成形体、並びにそれらの製造方法である。 The present invention relates to a continuous fiber reinforced resin molded product and a method for producing the same. More specifically, the present invention has high adhesive strength and affinity at the polar interface between the continuous reinforcing fiber and the synthetic resin, has few voids existing at the polar interface, and can exhibit sufficient strength. The loss tangent of the reinforced resin molded body and the continuous fiber reinforced resin molded body is sufficiently small, and the storage elasticity of the continuous fiber reinforced resin molded body and the continuous fiber reinforced resin molded body capable of exhibiting sufficient shock absorption is sufficiently large and sufficient. It is a continuous fiber reinforced resin molded body capable of exhibiting a high impact strength, a continuous fiber reinforced resin molded body having high resin impregnation property and high strength and rigidity, and a method for producing them.
各種機械や自動車等の構造部品、圧力容器、及び管状の構造物等には、マトリックス樹脂材料にガラス繊維等の強化材が添加された複合材料成形体が使用されている。特に強度の観点から強化繊維が連続繊維であり、成形サイクルの観点、リサイクル性の観点から、樹脂が熱可塑性樹脂である連続繊維強化樹脂成形体が望まれている。この連続繊維強化樹脂成形体としては、強化繊維に添加する集束剤を工夫しているもの(例えば、以下の特許文献1参照)、熱可塑性樹脂の融解温度(融点)と結晶化温度の差を工夫しているもの(例えば、以下の特許文献2参照)、樹脂材料に有機塩を加えているもの(例えば、以下の特許文献3参照)、成形前駆体の布帛を熱可塑性の樹脂で積層しているもの(例えば、以下の特許文献4参照)、強化繊維に先に低融点の熱可塑性樹脂を含浸させ、含浸性を向上させたもの(例えば、以下の特許文献5参照)、表面樹脂に融点の違う二種類の樹脂を用いることで層間剥離に良好な耐性を有するもの(例えば、以下の特許文献6参照)が提案されている。
For structural parts such as various machines and automobiles, pressure vessels, tubular structures, and the like, composite material molded bodies in which a reinforcing material such as glass fiber is added to a matrix resin material are used. In particular, from the viewpoint of strength, the reinforcing fiber is a continuous fiber, and from the viewpoint of a molding cycle and recyclability, a continuous fiber reinforced resin molded body in which the resin is a thermoplastic resin is desired. As this continuous fiber reinforced resin molded body, a sizing agent added to the reinforced fiber is devised (for example, see Patent Document 1 below), and the difference between the melting temperature (melting point) and the crystallization temperature of the thermoplastic resin is determined. Those devised (for example, see
しかしながら、本願発明者らが鋭意検討した結果、従来技術の連続繊維強化樹脂成形体では、いずれのも連続強化繊維、例えば、ガラス繊維とマトリックス樹脂の間の界面の接着力、親和性が低いため、繊維と樹脂の極界面の領域に空隙が多く、十分な強度が発現せず、高い強度が要求される箇所への利用に応えられる性能を備えていないことを発見した。また、従来技術の連続繊維強化樹脂成形体では、いずれのも損失正接が高いため、十分な衝撃吸収が発現せず、高い衝撃吸収が要求される箇所への利用に応えられる性能を備えていないこと、いずれのも貯蔵弾性率が低いため、十分な衝撃強度が発現せず、高い衝撃強度が要求される箇所への利用に応えられる性能を備えていないこと、連続強化繊維への樹脂含浸性が低く、樹脂と連続強化繊維との間の接着が不十分であり、強度や剛性といった物性や生産性に劣るものであることを発見した。
かかる従来技術の水準に鑑み、本発明が解決しようとする課題は、連続強化繊維と合成樹脂との間の極界面における接着力、親和性が高く、該極界面に存在する空隙が少なく、十分な強度を発現することができる連続繊維強化樹脂成形体、損失正接が低く、十分な衝撃強度を発現することができる連続繊維強化樹脂成形体、貯蔵弾性率が高く、十分な衝撃強度を発現することができる連続繊維強化樹脂成形体、並びに樹脂含浸性が高く、高い強度や剛性を有する連続繊維強化樹脂成形体、並びにそれらの製造方法を提供することである。However, as a result of diligent studies by the inventors of the present application, in all of the continuous fiber reinforced resin molded bodies of the prior art, the adhesive strength and affinity of the interface between the continuous reinforced fibers, for example, the glass fiber and the matrix resin are low. It was discovered that there are many voids in the region of the polar interface between the fiber and the resin, sufficient strength is not developed, and the performance is not suitable for use in places where high strength is required. In addition, the continuous fiber reinforced resin molded bodies of the prior art do not have sufficient shock absorption due to the high loss and rigidity, and do not have the performance to be used in places where high shock absorption is required. In all cases, since the storage elastic modulus is low, sufficient impact strength is not exhibited, and it does not have the performance to be used in places where high impact strength is required. It was found that the bond between the resin and the continuous reinforcing fiber was insufficient, and the physical properties such as strength and rigidity and productivity were inferior.
In view of the level of the prior art, the problems to be solved by the present invention are high adhesive strength and affinity at the polar interface between the continuous reinforcing fiber and the synthetic resin, and there are few voids existing at the polar interface, which is sufficient. Continuous fiber reinforced resin molded body capable of exhibiting high strength, continuous fiber reinforced resin molded body capable of exhibiting sufficient impact strength with low loss tangent, high storage elastic modulus, exhibiting sufficient impact strength It is an object of the present invention to provide a continuous fiber reinforced resin molded body that can be used, a continuous fiber reinforced resin molded body that has high resin impregnation property and high strength and rigidity, and a method for producing them.
本願発明者らは、かかる課題を解決すべく鋭意検討し実験を重ねた結果、連続強化繊維の製造において塗布されるサイジング剤(集束剤ともいう。)と樹脂の相性、成形中の密閉性、樹脂の流れ等を工夫することで、連続強化繊維と合成樹脂との間の極界面における空隙を極めて少なくすることにより、これを用いたプレス成形により高い強度や剛性を有する連続繊維強化樹脂成形体を製造することができることを、また、連続繊維強化樹脂成形体の損失正接を低くし、これを用いたプレス成形により高い衝撃吸収を有する連続繊維強化樹脂成形体を製造することができることを、連続繊維強化樹脂成形体の貯蔵弾性率を高くし、これを用いたプレス成形により高い衝撃強度を有する連続繊維強化樹脂成形体を製造することができることを、2種類以上の熱可塑性樹脂を有する連続繊維強化樹脂成形体において、連続強化繊維と樹脂の極界面領域における各樹脂の比率が、他の樹脂領域における各樹脂の比率と異なることで、連続繊維強化樹脂成形体が高い強度や剛性を発現することを、予想外に見出し、本発明を完成するに至ったものである。 As a result of diligent studies and experiments to solve these problems, the inventors of the present application have found that the sizing agent (also referred to as a sizing agent) applied in the production of continuous reinforcing fibers and the resin are compatible with each other, and the airtightness during molding. By devising the flow of the resin, etc., the voids at the polar interface between the continuous reinforcing fiber and the synthetic resin are extremely reduced, and the continuous fiber reinforced resin molded body having high strength and rigidity by press molding using this. Also, it is possible to manufacture a continuous fiber reinforced resin molded body having high impact absorption by press molding using the continuous fiber reinforced resin molded body with a low loss tangent. It is possible to produce a continuous fiber reinforced resin molded body having high impact strength by increasing the storage elasticity of the fiber reinforced resin molded body and press molding using the continuous fiber having two or more kinds of thermoplastic resins. In the reinforced resin molded body, the ratio of each resin in the polar interface region between the continuous reinforced fiber and the resin is different from the ratio of each resin in the other resin region, so that the continuous fiber reinforced resin molded body exhibits high strength and rigidity. This was unexpectedly found, and the present invention was completed.
すなわち、本発明は以下のとおりのものである。
[1]略丸断面の連続強化繊維と合成樹脂からなる連続繊維強化樹脂成形体であって、該連続強化繊維の長さ方向に直交する断面における該連続強化繊維1本と該合成樹脂との間の極界面において、該連続強化繊維の周縁部から、該連続強化繊維1本の半径の10分の1離れた周縁外側領域内の空隙率が10%以下であるところの連続強化繊維の本数が、連続強化繊維の総数の10%以上であることを特徴とする連続繊維強化樹脂成形体。
[2]前記空隙率が10%以下である連続強化繊維の本数が、前記連続強化繊維の総数の90%以上である、前記[1]に記載の連続繊維強化樹脂成形体。
[3]前記空隙率が1%以下である連続強化繊維の本数が、前記連続強化繊維の総数の90%以上である、前記[2]に記載の連続繊維強化樹脂成形体。
[4]前記連続繊維強化樹脂複合体中の合成樹脂含浸率が99%以上である、前記[1]~[3]のいずれかに記載の連続繊維強化樹脂成形体。
[5]前記連続強化繊維がガラス繊維であり、かつ、前記連続繊維強化樹脂成形体の引張応力が480Mpa以上である、前記[1]~[4]のいずれかに記載の連続繊維強化樹脂成形体。
[6]前記連続強化繊維がガラス繊維であり、かつ、前記連続繊維強化樹脂成形体の曲げ弾性率が22Gpa以上である、前記[1]~[5]のいずれかに記載の連続繊維強化樹脂成形体。
[7]熱可塑性樹脂と連続強化繊維を含み、ひねりモードの損失正接が0.11以下である、連続繊維強化樹脂成形体。
[8]前記損失正接のピークが78℃以上である、前記[7]に記載の連続繊維強化樹脂成形体。
[9]連続強化繊維と熱可塑性樹脂を含み、ひねりモードの貯蔵弾性率が3.4GPa以上である、連続繊維強化樹脂成形体。
[10]斜め方向に切削した際の前記貯蔵弾性率が直行方向に切削した際の前記貯蔵弾性率の1.5倍以上である、前記[9]に記載の連続繊維強化樹脂成形体。
[11]150℃における前記貯蔵弾性率が最大の前記貯蔵弾性率の25%以上である、前記[9]又は[10]に記載の連続繊維強化樹脂成形体。
[12]せん断粘度が330MPa・s-1以上である、前記[9]~[11]のいずれかに記載の連続繊維強化樹脂成形体。
[13]連続強化繊維と熱可塑性樹脂を含み、曲げ貯蔵弾性率が22GPa以上である、連続繊維強化樹脂成形体。
[14]150℃における曲げ貯蔵弾性率が30℃における貯蔵弾性率の76%以上である、前記[13]に記載の連続繊維強化樹脂成形体。
[15]斜めに切削した際の曲げ貯蔵弾性率保持率が58%以上である、前記[13]又は[14]に記載の連続繊維強化樹脂成形体。
[16]50℃における引張貯蔵弾性率が22GPa以上である、前記[13]~[15]のいずれかに記載の連続繊維強化樹脂成形体。
[17]引張損失正接の最大値が0.037以下である、前記[13]~[16]のいずれかに記載の連続繊維強化樹脂成形体。
[18]引張貯蔵弾性率と曲げ貯蔵弾性率の逆転する温度が95℃以上である、前記[13]~[17]のいずれかに記載の連続繊維強化樹脂成形体。
[19]{30℃における(引張貯蔵弾性率―曲げ貯蔵弾性率)}/{200℃における(曲げ貯蔵弾性率―引張貯蔵弾性率)}≧1である、前記[13]~[18]のいずれかに記載の連続繊維強化樹脂成形体。
[20]略丸断面の連続強化繊維と2種以上の熱可塑性樹脂からなる連続繊維強化樹脂成形体であって、該連続強化繊維の長さ方向に直交する断面における該連続強化繊維1本と該熱可塑性樹脂との間の極界面において、該連続強化繊維の周縁部から、該2種以上の連続強化繊維1本の半径の10分の1離れた周縁外側領域内では、該2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂以外の樹脂の占有割合が、該樹脂領域の全体として占有割合が最も高い樹脂の占有割合よりも高いが、該周縁外側領域以外の樹脂領域内では、該2種以上の熱可塑性樹脂の内、該樹脂領域の全体として占有割合が最も高い樹脂以外の各樹脂が均一に分散しているか又は混合していることを特徴とする連続繊維強化樹脂成形体。
[21]前記2種類以上の熱可塑性樹脂が海島構造を有する、前記[20]に記載の連続繊維強化樹脂成形体。
[22]前記2種以上の熱可塑性樹脂の内、融点が最も高い樹脂の融点と、融点が最も低い樹脂の融点との差が100℃以上である、前記[20]又は[21]に記載の連続繊維強化樹脂成形体。
[23]前記2種以上の熱可塑性樹脂の混合物の融点が、前記2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂の融点と実質的に同じである、前記[20]~[22]のいずれかに記載の連続繊維強化樹脂成形体。
[24]前記2種以上の熱可塑性樹脂の混合物の昇温融解ピーク温度と降温結晶化ピーク温度の差が、前記2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂の昇温融解ピーク温度と降温結晶化ピーク温度の差よりも小さい、前記[20]~[23]のいずれかに記載の連続繊維強化樹脂成形体。
[25]前記2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂と前記連続強化繊維との間の結合力よりも、該樹脂領域の全体として占有割合が最も高い樹脂以外の少なくとも一つの樹脂と前記連続強化繊維との間の結合力が大きい、前記[20]~[24]のいずれかに記載の連続繊維強化樹脂成形体。
[26]前記2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂と前記連続強化繊維との間の表面張力の差よりも、該樹脂領域の全体として占有割合が最も高い樹脂以外の少なくとも一つの樹脂と前記連続強化繊維との間の表面張力の差が小さい、前記[20]~[25]のいずれかに記載の連続繊維強化樹脂成形体。
[27]前記2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂の前記連続強化繊維に対する濡れ性よりも、該樹脂領域の全体として占有割合が最も高い樹脂以外の少なくとも一つの樹脂の前記連続強化繊維に対する濡れ性が高い、前記[20]~[26]のいずれかに記載の連続繊維強化樹脂成形体。
[28]以下の工程:
カップリング剤、結束剤、及び潤滑剤からなる集束剤が添加されている連続強化繊維と、該カップリング剤と反応性がある末端官能基を有する熱可塑性樹脂とを、該熱可塑性樹脂の融点以上となるように加熱プレスする工程;及び
これを該熱可塑性樹脂の融点以下まで冷却し、成形品として連続繊維強化樹脂複合材料を得る工程;
を含む、連続繊維強化樹脂複合材料の製造方法。
[29]前記熱可塑性樹脂の吸水率が0.1重量%以上である、前記[28]に記載の方法。
[30]前記集束剤の50重量%以上が加熱プレス中に、前記熱可塑性樹脂中に拡散する、前記[28]又は[29]に記載の方法。
[31]前記カップリング剤と熱可塑性樹脂の末端官能基が結合している、前記[28]~[30]のいずれかに記載の方法。
[32]前記連続繊維強化樹脂複合材料中の末端官能基の量が、前記熱可塑性樹脂中に含まれている末端官能基の量よりも少ない、前記[28]~[31]のいずれかに記載の方法。
[33]前記末端官能基の量が、前記熱可塑性樹脂中に含まれている末端官能基の量の90%以下である、前記[28]~[32]のいずれかに記載の方法。
[34]前記熱可塑性樹脂に含まれる粒子状添加材の含有量が30ppm以下である、前記[28]~[33]のいずれかに記載の方法。
[35]前記熱可塑性樹脂がポリアミド樹脂であり、前記カップリング剤と反応性がある末端官能基としての、該ポリアミド樹脂に含まれるカルボキシル基末端の量が65μmol/g以上である、前記[28]~[34]のいずれかに記載の方法。
[36]前記熱可塑性樹脂がポリアミド樹脂であり、前記カップリング剤と反応性がある末端官能基としての、該ポリアミド樹脂に含まれるアミノ基末端の量が40μmol/g以下である、前記[28]~[35]のいずれかに記載の方法。
[37]前記[28]~[36]のいずれかに記載の方法により製造された連続繊維強化樹脂複合材料を、前記熱可塑性樹脂の融点以上に加熱し、型を用いてプレスし、その後、該熱可塑性樹脂の融点以下の温度まで冷却して、賦形する工程を含む、連続繊維強化樹脂複合材料の賦形成形体の製造方法。
[38]冷却時に圧縮を行う、前記[37]に記載の方法。
[39]強化繊維と、該強化繊維とのμドロップ生成係数が10以上である熱可塑性樹脂とを、該熱可塑性樹脂の融点以上となるように、加熱プレスする工程及び、これを該熱可塑性樹脂の結晶化温度以下まで冷却する工程を含む、繊維強化樹脂成形体の製造方法。
[40]ガラス繊維とポリアミド樹脂からなる強化繊維樹脂成形体であって、前記繊維強化樹脂成形体を切削し、400g/cm2の力がかかるように研磨した際の研磨面をSEMにより観察した時に、該ガラス繊維の長さ方向に直交する断面におけるガラス繊維1本とポリアミド樹脂との間の極界面において、ガラス繊維の周縁部から、ガラス繊維1本の半径の10分の1離れた周縁外側領域内の空隙率が10%以下であるところのガラス繊維の本数が、ガラス繊維の総数の90%以上である、繊維強化樹脂成形体。
[41]前記ガラス繊維が連続繊維である、前記[40]に記載の連続繊維強化樹脂成形体。
[42]熱可塑性樹脂と連続ガラス強化繊維とからなる複合材料成形品からなる通信機器筺体であって、引張強度が、下記式(3):
長手方向の引張強度(MPa)×0.5+幅方向の引張強度(MPa)×0.5>500MPa 式(3)
の関係を満たし、曲げ弾性率が、下記式(4):
長手方向の曲げ弾性率(MPa)×0.5+幅方向曲げ弾性率(MPa)×0.5>30MPa 式(4)
の関係を満たし、かつ、KEC法により測定される電界シールド性が、周波数1GHz帯において、10dB以下であることを特徴とする、通信機器筐体。
[43]連続強化繊維と熱可塑性樹脂からなる連続繊維強化樹脂成形体であって、アコースティックエミッション法測定において、層間剥離起因の破壊発生強度が40MPa以上である、連続繊維強化樹脂成形体。
That is, the present invention is as follows.
[1] A continuous fiber reinforced resin molded body composed of a continuous reinforcing fiber having a substantially round cross section and a synthetic resin, wherein the continuous reinforcing fiber and the synthetic resin have a cross section orthogonal to the length direction of the continuous reinforcing fiber. At the polar interface between the fibers, the number of continuous reinforcing fibers having a void ratio of 10% or less in the outer peripheral region separated from the peripheral edge of the continuous reinforcing fiber by 1/10 of the radius of one continuous reinforcing fiber. However, the continuous fiber reinforced resin molded body is characterized in that it is 10% or more of the total number of continuous reinforcing fibers.
[2] The continuous fiber reinforced resin molded product according to the above [1], wherein the number of continuous reinforcing fibers having a porosity of 10% or less is 90% or more of the total number of the continuous reinforcing fibers.
[3] The continuous fiber reinforced resin molded product according to the above [2], wherein the number of continuous reinforcing fibers having a porosity of 1% or less is 90% or more of the total number of the continuous reinforcing fibers.
[4] The continuous fiber reinforced resin molded product according to any one of [1] to [3] above, wherein the synthetic resin impregnation rate in the continuous fiber reinforced resin composite is 99% or more.
[5] The continuous fiber reinforced resin molding according to any one of the above [1] to [4], wherein the continuous fiber reinforced fiber is a glass fiber and the tensile stress of the continuous fiber reinforced resin molded body is 480 MPa or more. body.
[6] The continuous fiber reinforced resin according to any one of [1] to [5] above, wherein the continuous reinforced fiber is glass fiber and the flexural modulus of the continuous fiber reinforced resin molded body is 22 Gpa or more. Molded body.
[7] A continuous fiber reinforced resin molded product containing a thermoplastic resin and continuous reinforcing fibers and having a loss tangent of 0.11 or less in a twist mode.
[8] The continuous fiber reinforced resin molded product according to the above [7], wherein the peak of the loss tangent is 78 ° C. or higher.
[9] A continuous fiber reinforced resin molded product containing continuous reinforcing fibers and a thermoplastic resin and having a storage elastic modulus of 3.4 GPa or more in a twist mode.
[10] The continuous fiber reinforced resin molded body according to the above [9], wherein the storage elastic modulus when cut in an oblique direction is 1.5 times or more the storage elastic modulus when cut in a perpendicular direction.
[11] The continuous fiber reinforced resin molded product according to the above [9] or [10], wherein the storage elastic modulus at 150 ° C. is 25% or more of the maximum storage elastic modulus.
[12] The continuous fiber reinforced resin molded product according to any one of [9] to [11] above, wherein the shear viscosity is 330 MPa · s -1 or more.
[13] A continuous fiber reinforced resin molded product containing continuous reinforcing fibers and a thermoplastic resin and having a bending storage elastic modulus of 22 GPa or more.
[14] The continuous fiber reinforced resin molded product according to the above [13], wherein the bending storage elastic modulus at 150 ° C. is 76% or more of the storage elastic modulus at 30 ° C.
[15] The continuous fiber reinforced resin molded product according to the above [13] or [14], which has a flexural modulus retention rate of 58% or more when cut diagonally.
[16] The continuous fiber reinforced resin molded product according to any one of [13] to [15] above, wherein the tensile storage elastic modulus at 50 ° C. is 22 GPa or more.
[17] The continuous fiber reinforced resin molded product according to any one of [13] to [16] above, wherein the maximum value of the tensile loss tangent is 0.037 or less.
[18] The continuous fiber reinforced resin molded product according to any one of [13] to [17] above, wherein the temperature at which the tensile storage elastic modulus and the bending storage elastic modulus are reversed is 95 ° C. or higher.
[19] {13] to [18] above, where {(tensile storage elastic modulus-bending storage elastic modulus)} / {(bending storage elastic modulus-tensile storage elastic modulus)} ≧ 1 at 30 ° C. The continuous fiber reinforced resin molded body according to any one.
[20] A continuous fiber reinforced resin molded body composed of a continuous reinforcing fiber having a substantially round cross section and two or more kinds of thermoplastic resins, and one continuous reinforcing fiber having a cross section orthogonal to the length direction of the continuous reinforcing fiber. At the polar interface with the thermoplastic resin, the two or more kinds are in the outer peripheral region separated by one tenth of the radius of one of the two or more kinds of continuous reinforcing fibers from the peripheral edge portion of the continuous reinforcing fiber. Of the thermoplastic resins in the above, the occupancy ratio of the resin other than the resin having the highest occupancy ratio as a whole of the resin region is higher than the occupancy ratio of the resin having the highest occupancy ratio as a whole of the resin region. In the resin region other than the above, among the two or more types of thermoplastic resins, each resin other than the resin having the highest occupancy ratio as a whole in the resin region is uniformly dispersed or mixed. Continuous fiber reinforced resin molded body.
[21] The continuous fiber reinforced resin molded product according to the above [20], wherein the two or more types of thermoplastic resins have a sea-island structure.
[22] The above-mentioned [20] or [21], wherein the difference between the melting point of the resin having the highest melting point and the melting point of the resin having the lowest melting point among the two or more kinds of thermoplastic resins is 100 ° C. or more. Continuous fiber reinforced resin molded body.
[23] The melting point of the mixture of the two or more kinds of thermoplastic resins is substantially the same as the melting point of the resin having the highest overall occupancy ratio of the resin region among the two or more kinds of thermoplastic resins. The continuous fiber reinforced resin molded product according to any one of [20] to [22].
[24] The difference between the temperature-increasing peak temperature and the temperature-decreasing crystallization peak temperature of the mixture of the two or more types of thermoplastic resins is the highest in the resin region as a whole among the two or more types of thermoplastic resins. The continuous fiber reinforced resin molded body according to any one of [20] to [23] above, which is smaller than the difference between the temperature rise and melt peak temperature and the temperature drop crystallization peak temperature of the resin.
[25] Among the two or more types of thermoplastic resins, the overall occupancy ratio of the resin region is the highest, rather than the binding force between the resin having the highest overall occupancy ratio and the continuous reinforcing fiber. The continuous fiber reinforced resin molded body according to any one of [20] to [24], wherein the bonding force between at least one resin other than the resin and the continuous reinforcing fiber is large.
[26] Of the two or more types of thermoplastic resins, the occupancy ratio of the resin region as a whole is larger than the difference in surface tension between the resin having the highest occupancy ratio as a whole of the resin region and the continuous reinforcing fiber. The continuous fiber reinforced resin molded product according to any one of [20] to [25], wherein the difference in surface tension between at least one resin other than the highest resin and the continuous reinforcing fiber is small.
[27] Of the two or more types of thermoplastic resins, the resin having the highest overall occupancy ratio in the resin region other than the resin having the highest overall occupancy ratio in the resin region, rather than the wettability to the continuous reinforcing fibers. The continuous fiber reinforced resin molded body according to any one of the above [20] to [26], which has high wettability to the continuous reinforcing fiber of at least one resin.
[28] The following steps:
The melting point of the thermoplastic resin is a continuous reinforcing fiber to which a sizing agent consisting of a coupling agent, a sizing agent, and a lubricant is added, and a thermoplastic resin having a terminal functional group reactive with the coupling agent. The step of heat-pressing so as to be as described above; and the step of cooling this to below the melting point of the thermoplastic resin to obtain a continuous fiber reinforced resin composite material as a molded product;
A method for manufacturing a continuous fiber reinforced resin composite material, including.
[29] The method according to the above [28], wherein the water absorption rate of the thermoplastic resin is 0.1% by weight or more.
[30] The method according to the above [28] or [29], wherein 50% by weight or more of the sizing agent diffuses into the thermoplastic resin during a heating press.
[31] The method according to any one of [28] to [30] above, wherein the coupling agent and the terminal functional group of the thermoplastic resin are bonded.
[32] In any of the above [28] to [31], the amount of the terminal functional group in the continuous fiber reinforced resin composite material is smaller than the amount of the terminal functional group contained in the thermoplastic resin. The method described.
[33] The method according to any one of [28] to [32], wherein the amount of the terminal functional group is 90% or less of the amount of the terminal functional group contained in the thermoplastic resin.
[34] The method according to any one of [28] to [33] above, wherein the content of the particulate additive contained in the thermoplastic resin is 30 ppm or less.
[35] The thermoplastic resin is a polyamide resin, and the amount of the carboxyl group terminal contained in the polyamide resin as a terminal functional group reactive with the coupling agent is 65 μmol / g or more. ] To [34].
[36] The thermoplastic resin is a polyamide resin, and the amount of amino group terminals contained in the polyamide resin as a terminal functional group reactive with the coupling agent is 40 μmol / g or less. ] To [35].
[37] The continuous fiber reinforced resin composite material produced by the method according to any one of [28] to [36] is heated to a temperature equal to or higher than the melting point of the thermoplastic resin, pressed using a mold, and then pressed. A method for producing a formed form of a continuous fiber reinforced resin composite material, which comprises a step of cooling to a temperature equal to or lower than the melting point of the thermoplastic resin and shaping.
[38] The method according to [37] above, wherein compression is performed during cooling.
[39] A step of heat-pressing a reinforcing fiber and a thermoplastic resin having a μ drop formation coefficient of 10 or more with the reinforcing fiber so as to be equal to or higher than the melting point of the thermoplastic resin, and the thermoplasticity thereof. A method for manufacturing a fiber-reinforced resin molded body, which comprises a step of cooling to a temperature below the crystallization temperature of the resin.
[40] A reinforced fiber resin molded body composed of glass fiber and polyamide resin, and the polished surface when the fiber reinforced resin molded body was cut and polished so as to apply a force of 400 g / cm 2 was observed by SEM. Occasionally, at the polar interface between a glass fiber and a polyamide resin in a cross section orthogonal to the length direction of the glass fiber, the peripheral edge of the glass fiber is separated from the peripheral edge of the glass fiber by one tenth of the radius of the glass fiber. A fiber-reinforced resin molded body in which the number of glass fibers in the outer region where the void ratio is 10% or less is 90% or more of the total number of glass fibers.
[41] The continuous fiber reinforced resin molded product according to the above [40], wherein the glass fiber is a continuous fiber.
[42] A communication device housing made of a composite material molded product made of a thermoplastic resin and continuous glass reinforced fibers, wherein the tensile strength is the following formula (3) :.
Longitudinal tensile strength (MPa) x 0.5 + Width tensile strength (MPa) x 0.5> 500 MPa Formula (3)
Satisfying the relationship of, the flexural modulus is the following equation (4):
Longitudinal flexural modulus (MPa) x 0.5 + Width flexural modulus (MPa) x 0.5> 30 MPa Formula (4)
A communication device housing characterized in that the electric field shielding property measured by the KEC method is 10 dB or less in a frequency band of 1 GHz.
[43] A continuous fiber reinforced resin molded body composed of a continuous reinforced fiber and a thermoplastic resin, wherein the fracture generation strength due to delamination is 40 MPa or more in the acoustic emission method measurement.
本発明に係る連続繊維強化樹脂成形体は、連続強化繊維と合成樹脂との間の極界面における接着力、親和性が高く、該極界面に存在する空隙が少なく、十分な強度や剛性、衝撃強度、高い長期特性を発現することができ、また、損失正接が十分小さく、十分な衝撃吸収を発現すること、貯蔵弾性率が十分大きく、十分な衝撃強度を発現すること、樹脂脂含浸性が高く、高い強度や剛性を発現することができる。 The continuous fiber reinforced resin molded body according to the present invention has high adhesive strength and affinity at the polar interface between the continuous reinforced fiber and the synthetic resin, has few voids existing at the polar interface, and has sufficient strength, rigidity, and impact. Strength, high long-term characteristics can be exhibited, loss tangent is sufficiently small, sufficient impact absorption is exhibited, storage elastic modulus is sufficiently large, sufficient impact strength is exhibited, and resin fat impregnation property is exhibited. It is high and can develop high strength and rigidity.
以下、本発明の実施形態について詳細に説明する。
[連続繊維強化樹脂成形体]
本実施形態の連続繊維強化樹脂成形体は、略丸断面の連続強化繊維と合成樹脂からなる連続繊維強化樹脂成形体であって、該連続強化繊維の長さ方向に直交する断面における該連続強化繊維1本と該合成樹脂との間の極界面において、該連続強化繊維の周縁部から、該連続強化繊維1本の半径の10分の1離れた周縁外側領域内の空隙率が10%以下であるところの連続強化繊維の本数が、連続強化繊維の総数の10%以上であること、また、動的粘弾性測定における、ひねりモードの損失正接(tanδ)が0.11以下であること、動的粘弾性測定における、ひねりモードの貯蔵弾性率が3.4GPa以上であること、曲げモードの貯蔵弾性率が22GPa以上であることが好ましい。また2種類以上の熱可塑性樹脂を使用する場合は、該連続強化繊維の長さ方向に直交する断面における該連続強化繊維1本と該熱可塑性樹脂との間の極界面において、該連続強化繊維の周縁部から、連続強化繊維1本の半径の10分の1離れた周縁外側領域(極界面領域ともいう。)内では、該2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂ともいう。)以外の樹脂(副樹脂ともいう。)の占有割合が、該樹脂領域の全体として占有割合が最も高い樹脂の占有割合よりも高いが、該周縁外側領域以外の樹脂領域(他の樹脂領域ともいう。)内では、該2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂以外の樹脂(副樹脂)が均一に分散しているか又は混合していることが好ましい。
また、本実施形態の連続繊維強化樹脂複合材料の製造方法は、以下の工程:
カップリング剤、結束剤、及び潤滑剤からなる集束剤が添加されている連続強化繊維と、該カップリング剤と反応性がある末端官能基を有する熱可塑性樹脂とを、該熱可塑性樹脂の融点以上となるように加熱プレスする工程;及び
これを該熱可塑性樹脂の融点以下まで冷却し、成形品として連続繊維強化樹脂複合材料を得る工程;
を含むことが好ましい。Hereinafter, embodiments of the present invention will be described in detail.
[Continuous fiber reinforced resin molded body]
The continuous fiber reinforced resin molded body of the present embodiment is a continuous fiber reinforced resin molded body composed of a continuously reinforced fiber having a substantially round cross section and a synthetic resin, and the continuous reinforced resin has a cross section orthogonal to the length direction of the continuous reinforced fiber. At the polar interface between one fiber and the synthetic resin, the void ratio in the peripheral outer peripheral region separated from the peripheral edge of the continuous reinforcing fiber by 1/10 of the radius of the continuous reinforcing fiber is 10% or less. The number of continuous reinforcing fibers is 10% or more of the total number of continuous reinforcing fibers, and the loss tangent (tan δ) in the twist mode in the dynamic viscoelastic modulus measurement is 0.11 or less. In the dynamic viscoelasticity measurement, it is preferable that the storage elastic modulus in the twist mode is 3.4 GPa or more and the storage elastic modulus in the bending mode is 22 GPa or more. When two or more kinds of thermoplastic resins are used, the continuous reinforcing fibers are formed at the polar interface between the continuous reinforcing fiber and the thermoplastic resin in a cross section orthogonal to the length direction of the continuous reinforcing fibers. Within the peripheral outer peripheral region (also referred to as the polar interface region) 1/10 of the radius of one continuous reinforcing fiber from the peripheral edge of the resin, the resin region as a whole is occupied among the two or more types of thermoplastic resins. The occupancy ratio of the resin (also referred to as the secondary resin) other than the resin having the highest ratio (also referred to as the main resin) is higher than the occupancy ratio of the resin having the highest occupancy ratio as a whole of the resin region, but the outside of the peripheral edge. In the resin region other than the region (also referred to as another resin region), among the two or more types of thermoplastic resins, the resin (secondary resin) other than the resin having the highest occupancy ratio as a whole in the resin region is uniformly dispersed. It is preferably mixed or mixed.
Further, the method for producing the continuous fiber reinforced resin composite material of the present embodiment is described in the following steps:
The melting point of the thermoplastic resin is a continuous reinforcing fiber to which a sizing agent consisting of a coupling agent, a sizing agent, and a lubricant is added, and a thermoplastic resin having a terminal functional group reactive with the coupling agent. The step of heat-pressing so as to be as described above; and the step of cooling this to below the melting point of the thermoplastic resin to obtain a continuous fiber reinforced resin composite material as a molded product;
Is preferably included.
すなわち、図1に示すように、本実施形態の連続繊維強化樹脂成形体は、略丸断面の連続強化繊維と合成樹脂からなる連続繊維強化樹脂成形体であり、該連続強化繊維の長さ方向に直交する断面における該連続強化繊維1本と該合成樹脂との間の極界面に観察される、該連続強化繊維の周縁部から、半径方向に、該連続強化繊維1本の半径rの10分の1(すなわち、r/10)離れた周縁外側領域(極界面領域ともいう。)内の空隙率が10%以下であるところの連続強化繊維が存在し、その本数は、連続強化繊維の総数の10%以上である。尚、連続強化繊維の断面は略丸断面であることが好ましいが、図1に示すように楕円形状であってもよい。その場合、「半径」とは、繊維断面の中心からの周縁部に向かう最短距離とする。
また、本実施形態の連続繊維強化樹脂成形体は、極界面領域内では、2種以上の熱可塑性樹脂の内、副樹脂の占有割合が、主樹脂の占有割合よりも高くなっていることが好ましい。この状態を図7に示す。That is, as shown in FIG. 1, the continuous fiber reinforced resin molded body of the present embodiment is a continuous fiber reinforced resin molded body composed of a continuous reinforced fiber having a substantially round cross section and a synthetic resin, and the continuous fiber reinforced resin molded body is in the length direction of the continuous reinforced fiber. 10 of the radius r of the continuous reinforcing fiber in the radial direction from the peripheral edge of the continuous reinforcing fiber observed at the polar interface between the continuous reinforcing fiber and the synthetic resin in the cross section orthogonal to There are continuous reinforcing fibers in which the void ratio in the outer peripheral region (also referred to as the polar interface region) separated by 1/10 (that is, r / 10) is 10% or less, and the number of the continuous reinforcing fibers is the same as that of the continuous reinforcing fibers. It is 10% or more of the total number. The cross section of the continuous reinforcing fiber is preferably a substantially round cross section, but may have an elliptical shape as shown in FIG. In that case, the "radius" is the shortest distance from the center of the fiber cross section toward the peripheral edge.
Further, in the continuous fiber reinforced resin molded product of the present embodiment, the occupancy ratio of the secondary resin among the two or more types of thermoplastic resins is higher than the occupancy ratio of the main resin in the polar interface region. preferable. This state is shown in FIG.
「連続強化繊維の長さ方向に直交する断面における該連続強化繊維1本と該合成樹脂との間の極界面に観察される、該連続強化繊維の周縁部から、該連続強化繊維1本の半径の10分の1離れた周縁外側領域」における空隙率は、例えば、バンドソー等により1cm角に切削した連続繊維強化樹脂成形体の連続強化繊維の長さ方向に直交する断面を、研磨面に400g/cm2の力がかかるように、研磨台を100rpmで回転させて、耐水ペーパー番手#220で10分間、耐水ペーパー番手#400で2分間、耐水ペーパー番手#800で5分間、耐水ペーパー番手#1200で10分間、耐水ペーパー番手#2000で15分間、炭化ケイ素フィルム粒度9μmで15分間、アルミナフィルム粒度5μmで15分間、アルミナフィルム粒度3μmで15分間、アルミナフィルム粒度1μmで15分間、バフ研磨紙発泡ポリウレタンを用いた粒度0.1μmのコロイダルシリカ(バイカロックス0.1CR)で10分間の順番で、各研磨で約7mL/minで水を加えながら研磨し、研磨したサンプルを、走査型電子顕微鏡(SEM)で観察し、ImageJ等のソフトにより画像解析することで、下記式:
空隙率(%)=(連続強化繊維の周縁部から該連続強化繊維の半径の10分の1離れた周縁外側領域内の空隙の面積)/(連続強化繊維の周縁部から該連続強化繊維の半径の10分の1離れた周縁外側領域の面積)×100
により求めることができる。"From the peripheral edge of the continuous reinforcing fiber observed at the polar interface between the continuous reinforcing fiber and the synthetic resin in the cross section orthogonal to the length direction of the continuous reinforcing fiber, the continuous reinforcing fiber of the continuous reinforcing fiber. The void ratio in the "peripheral outer region separated by 1/10 of the radius" is, for example, a cross section orthogonal to the length direction of the continuously reinforced fiber of the continuous fiber reinforced resin molded body cut into a 1 cm square by a band saw or the like on the polished surface. Rotate the polishing table at 100 rpm so that a force of 400 g / cm 2 is applied, with water resistant paper count # 220 for 10 minutes, water resistant paper count # 400 for 2 minutes, water resistant paper count # 800 for 5 minutes, and water resistant paper count. Buff polishing with # 1200 for 10 minutes, water resistant paper count # 2000 for 15 minutes, silicon carbide film particle size 9 μm for 15 minutes, alumina film particle size 5 μm for 15 minutes, alumina
Porosity (%) = (Area of voids in the peripheral outer region of the continuous reinforcing fiber 1/10 of the radius of the continuous reinforcing fiber) / (From the peripheral edge of the continuous reinforcing fiber to the continuous reinforcing fiber Area of outer peripheral area 1/10 of radius away) x 100
Can be obtained by.
まず、任意の略丸断面の連続強化繊維1本の連続強化繊維の周縁部から、半径の10分の1の距離、該連続強化繊維の周縁部から離れた周縁外側領域(単に、「連続強化繊維の直径の10分の1の領域」、「極界面領域」ともいう。)における空隙率を求め、これを任意の100本について観察する。本実施形態の成形体においては、成形体の剛性や強度を高めるという観点から、連続強化繊維の直径の10分の1の領域の空隙率が10%以下であるものが、100本の内10本以上、すなわち、10%以上であり、好ましくは20%以上、より好ましくは50%以上、さらにより好ましくは70%以上、最も好ましくは90%以上である。
また、本実施形態の成形体においては、成形体の剛性や強度を高めるという観点から、連続強化繊維の直径の10分の1の領域の空隙率は5%以下であることが好ましく、より好ましくは2%以下、さらに好ましくは1%以下である。First, a continuous reinforcing fiber having an arbitrary substantially round cross section, a distance of 1/10 of the radius from the peripheral edge of one continuous reinforcing fiber, and an outer peripheral region away from the peripheral edge of the continuous reinforcing fiber (simply, "continuous reinforcement". The void ratio in "a region of 1/10 of the diameter of the fiber" and "a polar interface region") is determined, and this is observed for any 100 fibers. In the molded body of the present embodiment, from the viewpoint of increasing the rigidity and strength of the molded body, 10 out of 100 pieces have a void ratio of 10% or less in a region of 1/10 of the diameter of the continuous reinforcing fiber. The number is 10 or more, that is, 10% or more, preferably 20% or more, more preferably 50% or more, still more preferably 70% or more, and most preferably 90% or more.
Further, in the molded body of the present embodiment, from the viewpoint of increasing the rigidity and strength of the molded body, the porosity of the region of 1/10 of the diameter of the continuous reinforcing fiber is preferably 5% or less, which is more preferable. Is 2% or less, more preferably 1% or less.
連続強化繊維の直径の10分の1の領域の空隙率が10%以下であるものが、100本の内10%以上とするためには、例えば、連続強化繊維がガラス繊維の場合、ガラス繊維の製造において塗布されるサイジング剤(集束剤)束剤と合成樹脂との間のμドロップ生成係数が10以上であり、相性が良いものを選択し、インロー型等成形中に型内を密閉できる成形方法や圧力を調整したダブルベルトプレスによる成形方法を選択することにより、樹脂の漏れ出しを防ぎ、連続繊維強化樹脂成形体のガラス繊維の占有体積(Vf、体積含有率ともいう)の成形前後の変化を小さくし、集束剤に適した温度条件で成形することが好ましい。 In order to make the void ratio in the region of 1/10 of the diameter of the continuous reinforcing fiber 10% or less to 10% or more out of 100, for example, when the continuous reinforcing fiber is glass fiber, the glass fiber. The μ drop generation coefficient between the sizing agent (focusing agent) bundling agent applied in the production of the above and the synthetic resin is 10 or more, and one with good compatibility can be selected and the inside of the mold can be sealed during molding such as inlay mold. By selecting a molding method or a molding method using a double belt press with adjusted pressure, it is possible to prevent resin leakage and before and after molding the occupied volume (Vf, volume content) of the glass fiber of the continuous fiber reinforced resin molded body. It is preferable to reduce the change in the amount of the fiber and to mold the fiber under temperature conditions suitable for the sizing agent.
ひねりモードの損失正接は、例えば、バンドソー等により連続繊維の0°、90°方向に切削した連続繊維強化樹脂成形体を、窒素雰囲気下、昇温速度一定でひねりモードの粘弾性測定を行い、損失正接のピークトップの値から算出することができる。本実施形態の連続繊維強化樹脂成形体のひねりモードの損失正接は0.11以下であると好ましく、0.10以下であると好ましく、0.095以下であるとより好ましく、0.090以下であると更に好ましく、0.087以下であると最も好ましい。 For the loss tangent in the twist mode, for example, a continuous fiber reinforced resin molded body cut in the 0 ° and 90 ° directions of the continuous fiber with a band saw or the like is measured for viscoelasticity in the twist mode at a constant temperature rise rate in a nitrogen atmosphere . It can be calculated from the value of the peak top of the loss tangent. The loss tangent in the twist mode of the continuous fiber reinforced resin molded product of the present embodiment is preferably 0.11 or less, preferably 0.10 or less, more preferably 0.095 or less, and 0.090 or less. If there is, it is more preferable, and it is most preferable that it is 0.087 or less.
本実施形態の連続繊維強化樹脂成形体のひねりモードの損失正接のピークトップを示す温度は78℃以上であることが好ましく、80℃以上であることがより好ましく、82℃以上であることが更に好ましく、84℃以上であることが最も好ましい。 The temperature showing the peak top of the loss tangent in the twist mode of the continuous fiber reinforced resin molded product of the present embodiment is preferably 78 ° C. or higher, more preferably 80 ° C. or higher, and further preferably 82 ° C. or higher. Most preferably, it is 84 ° C. or higher.
本実施形態の連続繊維強化樹脂成形体においては、前記損失正接を各温度に対してプロットした時、ピークトップが2つ出てくることが好ましく、前記二つのピークトップの差が、80℃以下であることが好ましく、60℃以下であることがより好ましく、50℃以下であることが更に好ましく、35℃以下であることが最も好ましい。 In the continuous fiber reinforced resin molded product of the present embodiment, when the loss tangent is plotted for each temperature, it is preferable that two peak tops appear, and the difference between the two peak tops is 80 ° C. or less. It is preferably 60 ° C. or lower, more preferably 50 ° C. or lower, and most preferably 35 ° C. or lower.
前記損失正接が0.11以下の連続繊維強化樹脂成形体を製造するには、例えば、連続強化繊維がガラス繊維の場合、ガラス繊維の製造において塗布されるサイジング剤(集束剤)束剤と合成樹脂との間のμドロップ生成係数が10以上であり、相性が良いものを選択し、インロー型等成形中に型内を密閉できる成形方法や圧力を調整したダブルベルトプレスによる成形方法を選択することにより、樹脂の漏れ出しを防ぎ、連続繊維強化樹脂成形体のガラス繊維の占有体積(Vf、体積含有率ともいう)の成形前後の変化を小さくし、集束剤に適した温度条件で成形することが好ましい。 In order to produce a continuous fiber reinforced resin molded body having a loss tangent of 0.11 or less, for example, when the continuous reinforced fiber is glass fiber, it is synthesized with a sizing agent (focusing agent) bundling agent applied in the production of glass fiber. Select a resin that has a μ drop generation coefficient of 10 or more and is compatible with the resin, and select a molding method that can seal the inside of the mold during molding such as in-row mold or a molding method that uses a double belt press with adjusted pressure. This prevents resin leakage, reduces the change in the occupied volume (Vf, also referred to as volume content) of the glass fiber of the continuous fiber reinforced resin molded body before and after molding, and molds under temperature conditions suitable for the sizing agent. Is preferable.
ひねりモードの貯蔵弾性率は、例えば、バンドソー等により連続繊維の0°、90°方向に切削した連続繊維強化樹脂成形体を、窒素雰囲気下、昇温速度一定でひねりモードの粘弾性測定を行い、各温度における貯蔵弾性率をプロットした際の貯蔵弾性率のピークトップの値から算出することができる。本実施形態の連続繊維強化樹脂成形体のひねりモードの貯蔵弾性率は3.4GPa以上であることが好ましく、3.5GPa以上であると好ましく、4.0GPa以上であるとより好ましく、4.5GPa以上であると更に好ましく、6.0GPa以上であると更に好ましく、7.0GPa以上であると最も好ましい。 For the storage elastic modulus in the twist mode, for example, a continuous fiber reinforced resin molded body cut in the 0 ° and 90 ° directions of the continuous fiber with a band saw or the like is measured for viscoelasticity in the twist mode at a constant temperature rise rate in a nitrogen atmosphere . , Can be calculated from the peak top value of the storage elastic modulus when plotting the storage elastic modulus at each temperature. The storage elastic modulus of the continuous fiber reinforced resin molded product of the present embodiment in the twist mode is preferably 3.4 GPa or more, preferably 3.5 GPa or more, more preferably 4.0 GPa or more, and 4.5 GPa or more. The above is more preferable, 6.0 GPa or more is further preferable, and 7.0 GPa or more is most preferable.
本実施形態の連続繊維強化樹脂成形体においては、前記貯蔵弾性率の測定を連続繊維強化樹脂成形体の連続繊維の45°方向(斜め方向)に切削した試験片を用いて行った際の前記貯蔵弾性率が、上記0°、90°方向に切削した試験片を用いて行った際の前記貯蔵弾性率の1.5倍以上であることが好ましく、1.6倍以上であるとより好ましく、1.7倍以上であると更に好ましく、1.9倍以上であると最も好ましい。 In the continuous fiber reinforced resin molded product of the present embodiment, the storage elastic modulus is measured by using a test piece cut in the 45 ° direction (diagonal direction) of the continuous fiber of the continuous fiber reinforced resin molded product. The storage elastic modulus is preferably 1.5 times or more, more preferably 1.6 times or more, the storage elastic modulus when the test piece cut in the 0 ° and 90 ° directions is used. It is more preferably 1.7 times or more, and most preferably 1.9 times or more.
本実施形態の連続繊維強化樹脂成形体においては、150℃における前記貯蔵弾性率が最大の前記貯蔵弾性率の25%以上であることが好ましく、26%以上であることがより好ましい。 In the continuous fiber reinforced resin molded product of the present embodiment, the storage elastic modulus at 150 ° C. is preferably 25% or more, more preferably 26% or more of the maximum storage elastic modulus.
本実施形態の連続繊維強化樹脂成形体においては、上記ひねりモードの粘弾性測定において、せん断粘度が330MPa・s-1以上であることが好ましく、470MPa・s-1以上であることがより好ましく、500MPa・s-1以上であることが更に好ましく、700MPa・s-1以上であることが最も好ましい。In the continuous fiber reinforced resin molded product of the present embodiment, the shear viscosity is preferably 330 MPa · s -1 or more, more preferably 470 MPa · s -1 or more in the viscoelasticity measurement in the twist mode. It is more preferably 500 MPa · s - 1 or more, and most preferably 700 MPa · s-1 or more.
ひねりモードの貯蔵弾性率が3.4GPa以上の連続繊維強化樹脂成形体を製造するには、例えば、連続強化繊維がガラス繊維の場合、ガラス繊維の製造において塗布されるサイジング剤(集束剤)と合成樹脂との間のμドロップ生成係数が10以上であり、相性が良いものを選択し、インロー型等成形中に型内を密閉できる成形方法や圧力を調整したダブルベルトプレスによる成形方法を選択することにより、樹脂の漏れ出しを防ぎ、連続繊維強化樹脂成形体のガラス繊維の占有体積(Vf、体積含有率ともいう)の成形前後の変化を小さくし、集束剤に適した温度条件で成形することが好ましい。 In order to produce a continuous fiber reinforced resin molded body having a storage elasticity of 3.4 GPa or more in the twist mode, for example, when the continuous reinforced fiber is glass fiber, it is combined with a sizing agent (focusing agent) applied in the production of glass fiber. Select one that has a μ drop generation coefficient of 10 or more with synthetic resin and is compatible with it, and select a molding method that can seal the inside of the mold during molding such as in-row mold and a molding method that uses a double belt press with adjusted pressure. By doing so, it is possible to prevent resin leakage, reduce the change in the occupied volume (Vf, also referred to as volume content) of the glass fiber of the continuous fiber reinforced resin molded body before and after molding, and mold under temperature conditions suitable for the sizing agent. It is preferable to do.
曲げ貯蔵弾性率は、例えば、バンドソー等により連続繊維の0°、90°方向に切削した連続繊維強化樹脂成形体を、窒素雰囲気下、昇温速度一定で曲げモードの粘弾性測定を行い、各温度における貯蔵弾性率をプロットした際の最大の貯蔵弾性率から算出することができる。本実施形態の連続繊維強化樹脂成形体の曲げ貯蔵弾性率は22GPa以上であることが好ましく、23GPa以上であると好ましく、25GPa以上であるとより好ましく、31GPa以上であると更に好ましく、36GPa以上であると最も好ましい。 For the flexural modulus of storage, for example, a continuous fiber reinforced resin molded body cut in the 0 ° and 90 ° directions of continuous fibers with a band saw or the like is measured for viscoelasticity in a bending mode at a constant temperature rise rate in a nitrogen atmosphere . It can be calculated from the maximum storage elastic modulus when plotting the storage elastic modulus at temperature. The flexural modulus of the continuous fiber reinforced resin molded product of the present embodiment is preferably 22 GPa or more, preferably 23 GPa or more, more preferably 25 GPa or more, further preferably 31 GPa or more, and 36 GPa or more. It is most preferable to have it.
本実施形態の連続繊維強化樹脂成形体においては、上記曲げ貯蔵弾性率の測定を150℃で行った際の曲げ貯蔵弾性率が30℃における曲げ貯蔵弾性率の76%以上であることが好ましい。 In the continuous fiber reinforced resin molded body of the present embodiment, the flexural modulus when the flexural modulus is measured at 150 ° C. is preferably 76% or more of the flexural modulus at 30 ° C.
本実施形態の連続繊維強化樹脂成形体においては、上記曲げ貯蔵弾性率の測定を連続繊維強化樹脂成形体の連続繊維の45°方向(斜め方向)に切削した試験片を用いて行った際の曲げ貯蔵弾性率が、上記0°、90°方向に切削した試験片を用いて行った際の貯蔵弾性率の58%以上であることが好ましく、60%以上であるとより好ましく、62%以上であると更に好ましい。 In the continuous fiber reinforced resin molded body of the present embodiment, the bending storage elastic modulus is measured by using a test piece cut in the 45 ° direction (diagonal direction) of the continuous fiber of the continuous fiber reinforced resin molded body. The flexural modulus of storage is preferably 58% or more, more preferably 60% or more, and 62% or more of the storage elastic modulus when the test pieces cut in the 0 ° and 90 ° directions are used. Is more preferable.
引張貯蔵弾性率と引張損失正接は、例えば、バンドソー等により連続繊維の0°、90°方向に切削した連続繊維強化樹脂成形体を、窒素雰囲気下、昇温速度一定で引張モードの粘弾性測定を行うことで求めることができる。本実施形態の連続繊維強化樹脂成形体においては、50℃における引張貯蔵弾性率は22GPa以上が好ましく、25GPa以上であると好ましく、30GPa以上であるとより好ましく、32GPa以上であると更に好ましく、35GPa以上であると更に好ましく、40GPa以上であると最も好ましい。 The tensile storage elastic modulus and the tangent of the tensile loss are measured by measuring the viscoelasticity of the continuous fiber reinforced resin molded body cut in the 0 ° and 90 ° directions of the continuous fiber with a band saw or the like at a constant temperature rise rate in a nitrogen atmosphere . Can be obtained by doing. In the continuous fiber reinforced resin molded product of the present embodiment, the tensile storage elastic modulus at 50 ° C. is preferably 22 GPa or more, preferably 25 GPa or more, more preferably 30 GPa or more, further preferably 32 GPa or more, still more preferably 35 GPa. The above is more preferable, and 40 GPa or more is most preferable.
最大の引張損失正接は上記測定により得られた各温度における損失正接をプロットした極大点で求めることができる。本実施形態の連続繊維強化樹脂成形体においては、最大の損失正接は、0.037以下であることが好ましく、0.035以下であることがより好ましく、0.032以下であることが更に好ましい。 The maximum tensile loss tangent can be obtained from the maximum point obtained by plotting the loss tangent at each temperature obtained by the above measurement. In the continuous fiber reinforced resin molded product of the present embodiment, the maximum loss tangent is preferably 0.037 or less, more preferably 0.035 or less, still more preferably 0.032 or less. ..
本実施形態の連続繊維強化樹脂成形体においては、引張貯蔵弾性率と曲げ貯蔵弾性率を各温度に対してプロットした際に、引張貯蔵弾性率と曲げ貯蔵弾性率の値が逆転する温度が95℃以上であることが好ましく、100℃以上であることがより好ましく、105℃以上であることが更に好ましい。 In the continuous fiber reinforced resin molded body of the present embodiment, when the tensile storage elastic modulus and the bending storage elastic modulus are plotted against each temperature, the temperature at which the values of the tensile storage elastic modulus and the bending storage elastic modulus are reversed is 95. The temperature is preferably ℃ or higher, more preferably 100 ℃ or higher, and even more preferably 105 ℃ or higher.
本実施形態の連続繊維強化樹脂成形体においては、引張貯蔵弾性率と曲げ貯蔵弾性率を各温度に対してプロットした際に、以下の式:
{30℃における(引張貯蔵弾性率―曲げ貯蔵弾性率)}/{200℃における(曲げ貯蔵弾性率―引張貯蔵弾性率)}≧1
を満たすことが好ましい。In the continuous fiber reinforced resin molded body of the present embodiment, when the tensile storage elastic modulus and the bending storage elastic modulus are plotted for each temperature, the following formula:
{(Tension storage elastic modulus-Bending storage elastic modulus) at 30 ° C} / {(Bending storage elastic modulus-Tension storage elastic modulus) at 200 ° C} ≧ 1
It is preferable to satisfy.
曲げ貯蔵弾性率が22GPa以上の連続繊維強化樹脂成形体を製造するには、例えば、連続強化繊維がガラス繊維の場合、ガラス繊維の製造において塗布されるサイジング剤(集束剤)と合成樹脂との間のμドロップ生成係数が10以上であり、相性が良いものを選択し、インロー型等成形中に型内を密閉し樹脂の流動を抑制できる成形方法や圧力を調整したダブルベルトプレスによる成形方法を選択することにより、樹脂の漏れ出しを防ぎ、連続繊維強化樹脂成形体のガラス繊維の占有体積(Vf、体積含有率ともいう)の成形前後の変化を小さくし、集束剤に適した温度条件で良好な界面を形成しながら成形することが好ましい。 In order to produce a continuous fiber reinforced resin molded body having a bending storage elasticity of 22 GPa or more, for example, when the continuous reinforced fiber is glass fiber, a sizing agent (focusing agent) applied in the production of glass fiber and a synthetic resin are used. A molding method that can suppress the flow of resin by sealing the inside of the mold during molding such as in-row mold, or a molding method by double belt press that adjusts the pressure, by selecting one with a μ drop generation coefficient of 10 or more and good compatibility. By selecting, the leakage of resin is prevented, the change in the occupied volume (Vf, also referred to as volume content) of the glass fiber of the continuous fiber reinforced resin molded body before and after molding is reduced, and the temperature conditions suitable for the sizing agent are reduced. It is preferable to mold while forming a good interface.
本実施形態の連続繊維強化樹脂成形体における前記周縁外側領域内での、各熱可塑性樹脂の占有割合(面積比率)は、例えば、連続繊維強化樹脂成形体の厚さ方向断面(連続強化繊維の長さ方向に直交する断面)について切り出し、エポキシ樹脂に包埋し、連続強化繊維が破損しないように注意しながら研磨を行った後、レーザーラマン顕微鏡により該断面のマッピング画像を撮影し、得られた画像、スペクトルから、繊維強化樹脂に含まれる樹脂の種類を特定し、それぞれの面積をImageJによる画像処理によって算出することができる。
また、繊維強化樹脂成形体における極界面領域以外の樹脂領域内での熱可塑性樹脂の分布は、例えば、厚さ方向断面(連続強化繊維の長さ方向に直交する断面)に切削した連続繊維強化樹脂成形体の断面(連続強化繊維の長さ方向に直交する断面)を、研磨面に125g/cm2の力がかかるように、耐水ペーパー番手#220で10分間、耐水ペーパー番手#1200で10分間耐水ペーパー番手#2000で5分間、炭化ケイ素フィルム粒度9μmで10分間、アルミナフィルム粒度5μmで10分間、アルミナフィルム粒度3μmで5分間、アルミナフィルム粒度1μmで5分間、バフ研磨紙発泡ポリウレタンを用いた粒度0.1μmのコロイダルシリカ(バイカロックス0.1CR)で5分間の順番で、各研磨で約7mL/minで水を加えながら研磨し、研磨したサンプルを、リンタングステン酸等で電子染色した後、走査型電子顕微鏡(SEM)で観察し、ImageJ等のソフトにより画像解析することで、求めることができる。熱可塑性樹脂の占有割合は任意の10点を観察して、その平均から求めることができる。The occupancy ratio (area ratio) of each thermoplastic resin in the peripheral outer region of the continuous fiber reinforced resin molded body of the present embodiment is, for example, a cross section in the thickness direction of the continuous fiber reinforced resin molded body (continuously reinforced fiber). (Cross section orthogonal to the length direction) is cut out, embedded in epoxy resin, polished while being careful not to damage the continuous reinforcing fibers, and then a mapping image of the cross section is taken with a laser Raman microscope to obtain it. The type of resin contained in the fiber reinforced resin can be specified from the images and spectra, and the respective areas can be calculated by image processing by ImageJ.
Further, the distribution of the thermoplastic resin in the resin region other than the polar interface region in the fiber-reinforced resin molded body is, for example, continuous fiber reinforcement cut in a thickness direction cross section (a cross section orthogonal to the length direction of the continuous reinforcing fiber). The cross section of the resin molded body (cross section orthogonal to the length direction of the continuous reinforcing fiber) is 10 minutes with water resistant paper count # 220 and 10 with water resistant paper count # 1200 so that a force of 125 g / cm 2 is applied to the polished surface. Minutes Water resistant paper count # 2000 for 5 minutes, Silicon carbide film grain size 9 μm for 10 minutes, Alumina film grain size 5 μm for 10 minutes, Alumina
連続強化繊維と合成樹脂、例えば、熱可塑性樹脂との体積比率は、Vfが高い程、成形体の強度は高くなるため、本実施形態の連続繊維強化樹脂成形体は、連続繊維強化樹脂成形体中の連続強化繊維の体積含有率Vfが40%以上のものが好ましく、45%以上のものがより好ましく、50%以上のものが更に好ましく、55%以上のものがより更に好ましく、65%以上であるものが最も好ましい。従来技術の繊維強化樹脂成形体では、Vfを高くしても、前記した空隙率が高く、成形品の引張応力(引張強度)や曲げ弾性率(曲げ剛性)を高くすることができなかったが、本実施形態の連続繊維強化樹脂成形体では、空隙率を少なくすることにより、Vf50%で、連続繊維強化樹脂複合体中の合成樹脂含浸率99%以上、引張応力525Mpa以上、曲げ弾性率27Gpa以上、Vf65%で合成樹脂含浸率99%以上、引張応力600MPa以上、曲げ弾性率35GPa以上を同時に達成している。
連続強化繊維がガラス繊維である場合には、連続繊維強化樹脂成形体の引張応力は、ガラス繊維が実質的に配向している各方向で試験した際の平均値として480MPa以上が好ましく、525MPa以上がより好ましく、600MPa以上が更に好ましく、620MPa以上が最も好ましい。また連続繊維強化樹脂成形体の曲げ弾性率は、ガラス繊維が実質的に配向している各方向で試験した際の平均値として22GPa以上が好ましく、27GPa以上がより好ましく、30GPa以上が更に好ましく、35GPa以上が最も好ましい。この時、引張応力と曲げ弾性率は、連続繊維強化樹脂成形体に含まれる連続強化繊維が実質的に二方向に配向している場合の値であり、連続強化繊維に平行な二方向について試験した値の平均値である。三方向材の場合には、2/3倍の応力又は剛性であることが好ましく、n方向材の場合は2/n倍の応力又は剛性であることが好ましい。As for the volume ratio between the continuously reinforced fiber and the synthetic resin, for example, the thermoplastic resin, the higher the Vf, the higher the strength of the molded body. Therefore, the continuous fiber reinforced resin molded body of the present embodiment is a continuous fiber reinforced resin molded body. The volume content Vf of the continuous reinforcing fibers in the fiber is preferably 40% or more, more preferably 45% or more, further preferably 50% or more, further preferably 55% or more, and 65% or more. Is the most preferable. In the conventional fiber-reinforced resin molded body, even if Vf is increased, the above-mentioned void ratio is high, and the tensile stress (tensile strength) and bending elastic modulus (bending rigidity) of the molded product cannot be increased. In the continuous fiber reinforced resin molded body of the present embodiment, by reducing the void ratio, the synthetic resin impregnation rate in the continuous fiber reinforced resin composite is 99% or more, the tensile stress is 525 Mpa or more, and the flexural modulus is 27 Gpa at Vf 50%. As described above, the synthetic resin impregnation rate of 99% or more, the tensile stress of 600 MPa or more, and the bending elastic modulus of 35 GPa or more are simultaneously achieved at Vf 65%.
When the continuous reinforcing fiber is a glass fiber, the tensile stress of the continuous fiber reinforced resin molded body is preferably 480 MPa or more as an average value when tested in each direction in which the glass fiber is substantially oriented, and 525 MPa or more. Is more preferable, 600 MPa or more is further preferable, and 620 MPa or more is most preferable. The flexural modulus of the continuous fiber reinforced resin molded product is preferably 22 GPa or more, more preferably 27 GPa or more, still more preferably 30 GPa or more, as an average value when tested in each direction in which the glass fibers are substantially oriented. 35 GPa or more is most preferable. At this time, the tensile stress and the flexural modulus are the values when the continuous reinforcing fibers contained in the continuous fiber reinforced resin molded body are substantially oriented in two directions, and are tested in two directions parallel to the continuous reinforcing fibers. It is the average value of the values. In the case of a tridirectional material, the stress or rigidity is preferably 2/3 times, and in the case of an n-direction material, the stress or rigidity is preferably 2/n times.
連続強化繊維がガラス繊維である場合には、連続繊維強化樹脂成形体のガラス繊維が実質的に配向している各方向で試験した際の引張応力の平均値に、ガラス繊維が実質的に配向している方向の数を、乗じた値は960MPa以上が好ましく、1050MPa以上がより好ましく、1200MPa以上が更に好ましく、1240MPa以上が最も好ましい。また連続繊維強化樹脂成形体のガラス繊維が実質的に配向している各方向で試験した際の曲げ応力の平均値に、ガラス繊維が実質的に配向している数を、乗じた値は1260MPa以上が好ましく、1400MPa以上がより好ましく、1600MPa以上が更に好ましく、1700MPa以上が最も好ましい。また連続繊維強化樹脂成形体の曲げ弾性率をガラス繊維が実質的に配向している方向の数で乗じた値は44GPa以上が好ましく、54GPa以上がより好ましく、60GPa以上が更に好ましく、70GPa以上が最も好ましい。また連続繊維強化樹脂成形体の以下の式:
弾性指数=(ガラス繊維が実質的に配向している方向に平行方向の弾性率の平均値×ガラス繊維が実質的に配向している方向数)/(Vf×ガラス繊維の弾性率)
で定義される弾性指数が1.2以上であることが好ましく、1.3以上であることがより好ましく、1.4以上であることが更に好ましく、1.5以上であることがより更に好ましく、1.58以上であることが最も好ましい。When the continuous reinforcing fiber is a glass fiber, the glass fiber is substantially oriented to the average value of the tensile stress when the glass fiber of the continuous fiber reinforced resin molded body is tested in each direction in which the glass fiber is substantially oriented. The value obtained by multiplying the number in the direction of fiberglass is preferably 960 MPa or more, more preferably 1050 MPa or more, further preferably 1200 MPa or more, and most preferably 1240 MPa or more. Further, the value obtained by multiplying the average value of the bending stress in each direction in which the glass fibers of the continuous fiber reinforced resin molded body are substantially oriented by the number of substantially oriented glass fibers is 1260 MPa. The above is preferable, 1400 MPa or more is more preferable, 1600 MPa or more is further preferable, and 1700 MPa or more is most preferable. Further, the value obtained by multiplying the flexural modulus of the continuous fiber reinforced resin molded body by the number of directions in which the glass fibers are substantially oriented is preferably 44 GPa or more, more preferably 54 GPa or more, further preferably 60 GPa or more, and 70 GPa or more. Most preferred. In addition, the following formula of continuous fiber reinforced resin molded body:
Elastic modulus = (average value of elastic modulus in the direction parallel to the direction in which the glass fiber is substantially oriented × number of directions in which the glass fiber is substantially oriented) / (Vf × elastic modulus of glass fiber)
The elasticity index defined in is preferably 1.2 or more, more preferably 1.3 or more, further preferably 1.4 or more, and even more preferably 1.5 or more. , 1.58 or more is most preferable.
[アコースティックエミッション(AE)法測定]
本実施形態の連続繊維強化樹脂成形体は、アコースティックエミッション法測定において、層間剥離起因の破壊発生強度が40MPa以上であることが好ましく、50MPa以上であることがより好ましい。
アコースティックエミッション法測定は、層間せん断試験(JIS K7078)において、AEセンサーを取り付けることにより、実施できる。[Measurement by acoustic emission (AE) method]
In the acoustic emission method measurement, the continuous fiber reinforced resin molded product of the present embodiment preferably has a fracture generation strength of 40 MPa or more due to delamination, and more preferably 50 MPa or more.
The acoustic emission method measurement can be carried out by attaching an AE sensor in the interlayer shear test (JIS K7078).
[連続繊維強化樹脂成形体の形態]
連続繊維強化樹脂成形体の形態は、特に制限されず、以下の種々の形態が挙げられる。例えば、強化繊維の織物や編み物、組紐、パイプ状のものと樹脂を複合化した形態や、一方向に引き揃えた強化繊維と樹脂を複合化した形態、強化繊維と樹脂からなる糸を一方向に引き揃えて成形した形態、強化繊維と樹脂からなる糸を織物や編み物、組紐、パイプ状にして成形した形態が挙げられる。
連続繊維強化樹脂成形体の成形前の中間材料の形態としては、連続強化繊維と樹脂繊維との混繊糸、連続強化繊維の束の周囲を樹脂で被覆したコーティング糸、連続強化繊維に予め樹脂を含浸させテープ状にしたもの、連続強化繊維を樹脂のフィルムで挟んだもの、連続強化繊維に樹脂パウダーを付着させたもの、連続強化繊維の束を芯材としてその周囲を樹脂繊維で組紐としたもの、強化繊維束の間に予め樹脂を含浸させたもの等が挙げられる。[Form of continuous fiber reinforced resin molded body]
The form of the continuous fiber reinforced resin molded product is not particularly limited, and examples thereof include the following various forms. For example, a woven or knitted fabric of reinforcing fibers, a braid, a form in which a pipe-shaped material and a resin are combined, a form in which a reinforcing fiber and a resin are combined in one direction, and a thread made of a reinforcing fiber and a resin are used in one direction. Examples thereof include a form in which the yarns made of reinforcing fibers and a resin are formed into a woven fabric, a knitted fabric, a braid, or a pipe.
As the form of the intermediate material before molding of the continuous fiber reinforced resin molded body, a mixed fiber thread of the continuous reinforced fiber and the resin fiber, a coating thread in which the circumference of the bundle of the continuous reinforced fiber is coated with resin, and a resin in advance for the continuous reinforced fiber. Impregnated into a tape, continuous reinforcing fibers sandwiched between resin films, continuous reinforcing fibers with resin powder attached, a bundle of continuous reinforcing fibers as a core material, and a braid with resin fibers around it. Examples thereof include those obtained by impregnating the reinforcing fiber bundles with a resin in advance.
[連続繊維強化樹脂成形体(複合材料)の製造方法]
本実施形態の連続繊維強化樹脂複合材料の製造方法は、以下の工程:
カップリング剤、結束剤、及び潤滑剤からなる集束剤が添加されている連続強化繊維と、該カップリング剤と反応性がある末端官能基を有する熱可塑性樹脂とを、該熱可塑性樹脂の融点以上となるように加熱プレスする工程;及び
これを該熱可塑性樹脂の融点以下まで冷却し、成形品として連続繊維強化樹脂複合材料を得る工程;
を含むことが好ましい。
加熱プレス後の連続繊維強化樹脂複合材料の末端官能基の量が加熱プレス前の熱可塑性樹脂に含まれる末端官能基の量よりも少ないことが、熱可塑性樹脂と連続強化繊維との間の接着性の観点から好ましく、加熱プレス後の連続繊維強化樹脂複合材料の末端官能基の量が加熱プレス前の熱可塑性樹脂に含まれる末端官能基の量の90%以下であることがより好ましく、85%以下であることがより好ましい。
集束剤のカップリング剤と、熱可塑性樹脂の末端官能基との反応性の観点から、加熱プレス中の熱可塑性樹脂の流動率が10%以下であることが好ましく、8%以下であることがより好ましく、5%以下であることが更に好ましく、3%以下であることが最も好ましい。
反応性末端官能基は、例えば、熱可塑性樹脂としてポリプロピレンを用いた際には、主成分であるポリプロピレン樹脂にマレイン酸等がグラフトしたものでもよい。[Manufacturing method of continuous fiber reinforced resin molded body (composite material)]
The method for producing the continuous fiber reinforced resin composite material of the present embodiment is as follows:
The melting point of the thermoplastic resin is a continuous reinforcing fiber to which a sizing agent consisting of a coupling agent, a sizing agent, and a lubricant is added, and a thermoplastic resin having a terminal functional group reactive with the coupling agent. The step of heat-pressing so as to be as described above; and the step of cooling this to below the melting point of the thermoplastic resin to obtain a continuous fiber reinforced resin composite material as a molded product;
Is preferably included.
Adhesion between the thermoplastic resin and the continuous reinforcing fiber means that the amount of terminal functional groups in the continuous fiber reinforced resin composite material after heat pressing is less than the amount of terminal functional groups contained in the thermoplastic resin before heating pressing. From the viewpoint of properties, it is preferable that the amount of terminal functional groups in the continuous fiber reinforced resin composite material after heat pressing is 90% or less of the amount of terminal functional groups contained in the thermoplastic resin before heat pressing, more preferably 85. % Or less is more preferable.
From the viewpoint of the reactivity between the coupling agent of the sizing agent and the terminal functional group of the thermoplastic resin, the flow rate of the thermoplastic resin in the heat press is preferably 10% or less, preferably 8% or less. More preferably, it is more preferably 5% or less, and most preferably 3% or less.
As the reactive terminal functional group, for example, when polypropylene is used as the thermoplastic resin, maleic acid or the like may be grafted on the polypropylene resin as the main component.
加熱プレス中の熱可塑性樹脂の流動率は、(加熱プレス中に生じた熱可塑性樹脂のバリの重量)/(加熱プレス前の熱可塑性樹脂の重量)で求められる。
加熱プレスの方法は特に限定されないが、ダブルベルトプレスによる加熱プレス方法が生産性の観点から好ましい。基材は複数のロールから強化繊維と熱可塑性樹脂を繰り出してダブルベルトプレス装置に投入してもよいし、所望の大きさにカットした強化繊維と熱可塑性樹脂を所望の枚数重ねて投入してもよい。この時基材の前後に誘導用のシート等、例えばテフロン(登録商標)シートを一緒に投入してもよい。
その他の加熱プレス方法としては金型で行うことが好ましく挙げられる。金型で行うプレス方法は特に制限されず、以下の種々の方法が挙げられる。例えば、連続繊維強化樹脂成形体を構成する基材を、所望の成形体に合わせて裁断し、目的とする製品の厚みを考慮して必要枚数積層させ、金型形状に合わせてセットする。
基材の裁断は、1枚ずつ行ってもよいし、所望の枚数を重ねてから行ってもよい。生産性の観点からは、重ねた状態で裁断することが好ましい。裁断する方法は任意の方法でよく、例えば、ウォータージェット、刃プレス機、熱刃プレス機、レーザー、プロッター等があげられる。断面形状にすぐれ、更に、複数を重ねて裁断する際に端面を溶着することで取扱い性がよくなる熱刃プレス機が好ましい。適切な裁断形状は、トライアンドエラーを繰り返すことでも調整できるが、金型の形状にあわせてCAE(computer aided engineering)によるシミュレーションを行うことで設定することが好ましい。The flow rate of the thermoplastic resin in the heat press is determined by (weight of burrs of the thermoplastic resin generated in the heat press) / (weight of the thermoplastic resin before the heat press).
The method of hot pressing is not particularly limited, but the hot pressing method by double belt pressing is preferable from the viewpoint of productivity. As the base material, the reinforcing fibers and the thermoplastic resin may be fed out from a plurality of rolls and charged into the double belt press device, or the reinforcing fibers cut to a desired size and the thermoplastic resin may be loaded in a desired number of layers. May be good. At this time, a Teflon (registered trademark) sheet, for example, a Teflon (registered trademark) sheet, for example, may be put together before and after the base material.
As another heating pressing method, it is preferable to use a die. The pressing method performed by the die is not particularly limited, and the following various methods can be mentioned. For example, the base material constituting the continuous fiber reinforced resin molded body is cut according to a desired molded body, a required number of layers are laminated in consideration of the thickness of the target product, and the base material is set according to the mold shape.
The substrate may be cut one by one, or may be cut after stacking a desired number of sheets. From the viewpoint of productivity, it is preferable to cut in a stacked state. The cutting method may be any method, and examples thereof include a water jet, a blade press, a hot blade press, a laser, and a plotter. A hot blade press machine having an excellent cross-sectional shape and further improving handleability by welding end faces when cutting a plurality of layers is preferable. The appropriate cut shape can be adjusted by repeating trial and error, but it is preferable to set it by performing a simulation by CAE (computer aided engineering) according to the shape of the mold.
基材を金型にセットした後に金型を閉じてプレス(圧縮)する。そして、連続繊維強化樹脂成形体を構成する熱可塑性樹脂の融点以上の温度に金型を温調して熱可塑性樹脂を溶融させ賦型する。型締め圧力に特に規定はないが、好ましくは1MPa以上、より好ましくは3MPa以上である。また、ガス抜き等をするために一旦型締めをし、圧縮成形した後に一旦金型の型締め圧力を解除してもよい。圧縮成形の時間は、強度発現の観点からは、使用される熱可塑性樹脂が熱劣化しない範囲で長いほうが好ましいが、生産性の観点からは、好ましくは2分以内、より好ましくは1分以内が適している。
連続繊維強化樹脂成形体の製造工程においては、金型内に基材をセットして金型を閉じ、加圧し、所定の時間後に、更に所定の熱可塑性樹脂組成物を射出充填して成形し、熱可塑性樹脂と、所定の熱可塑性樹脂組成物とを接合させることにより、ハイブリッド成形体を製造してもよい。After setting the base material in the mold, the mold is closed and pressed (compressed). Then, the mold is temperature-controlled to a temperature equal to or higher than the melting point of the thermoplastic resin constituting the continuous fiber reinforced resin molded body to melt the thermoplastic resin and mold it. The mold clamping pressure is not particularly specified, but is preferably 1 MPa or more, more preferably 3 MPa or more. Further, the mold may be temporarily fastened for degassing or the like, and the mold tightening pressure may be released once after compression molding. From the viewpoint of strength development, the compression molding time is preferably long as long as the thermoplastic resin used does not deteriorate due to heat, but from the viewpoint of productivity, it is preferably within 2 minutes, more preferably within 1 minute. Is suitable.
In the manufacturing process of a continuous fiber reinforced resin molded product, a base material is set in a mold, the mold is closed, pressure is applied, and after a predetermined time, a predetermined thermoplastic resin composition is further injection-filled and molded. , A hybrid molded product may be produced by joining a thermoplastic resin and a predetermined thermoplastic resin composition.
所定の熱可塑性樹脂組成物を射出充填するタイミングは、両熱可塑性樹脂間の界面強度に大きく影響する。所定の熱可塑性樹脂組成物を射出充填するタイミングは、基材を金型内にセットして金型を閉じた後に金型温度が熱可塑性樹脂の融点、ガラス転移温度以上に昇温してから、30秒以内が好ましい。
所定の熱可塑性樹脂組成物を射出充填する時の金型温度は、連続繊維強化樹脂成形体を構成する熱可塑性樹脂の融点以上又はガラス転移温度以上であることが好ましい。より好ましくは、連続繊維強化樹脂成形体を構成する熱可塑性樹脂の融点+10℃以上又はガラス転移温度+10℃以上であり、更に好ましくは、融点+20℃以上又はガラス転移温度+20℃以上、更により好ましくは融点+30℃以上又はガラス転移温度+30℃以上である。The timing of injection filling of a predetermined thermoplastic resin composition greatly affects the interfacial strength between the two thermoplastic resins. The timing for injecting and filling the predetermined thermoplastic resin composition is after the base material is set in the mold and the mold is closed, and then the mold temperature rises above the melting point of the thermoplastic resin and the glass transition temperature. , 30 seconds or less is preferable.
The mold temperature when the predetermined thermoplastic resin composition is injection-filled is preferably equal to or higher than the melting point of the thermoplastic resin constituting the continuous fiber reinforced resin molded product or higher than the glass transition temperature. More preferably, the melting point of the thermoplastic resin constituting the continuous fiber reinforced resin molded body is + 10 ° C. or higher or the glass transition temperature is + 10 ° C. or higher, and even more preferably, the melting point is + 20 ° C. or higher or the glass transition temperature is + 20 ° C. or higher. Is a melting point of + 30 ° C. or higher or a glass transition temperature of + 30 ° C. or higher.
ハイブリッド成形体において、連続繊維強化樹脂成形体を構成する熱可塑性樹脂と、射出成形により形成された熱可塑性樹脂組成物の接合部分は、互いに混じり合った凹凸構造となっていることが好ましい。
金型温度を射出する熱可塑性樹脂組成物の融点以上とし、射出成形時の樹脂保圧を高く、例えば、1MPa以上とすることは界面強度を高める上で有効である。界面強度を高めるためには、保圧を5MPa以上とすることが好ましく、10MPa以上とすることがより好ましい。
保圧時間を長く、例えば5秒以上、好ましくは10秒以上、より好ましくは金型温度が熱可塑性樹脂組成物の融点以下になるまでの間の時間保持することは、界面強度を高める観点から好ましい。In the hybrid molded body, it is preferable that the bonded portion of the thermoplastic resin constituting the continuous fiber reinforced resin molded body and the thermoplastic resin composition formed by injection molding has a concavo-convex structure in which they are mixed with each other.
It is effective to set the temperature of the mold to be equal to or higher than the melting point of the thermoplastic resin composition to be injected and to increase the resin holding pressure at the time of injection molding, for example, to be 1 MPa or higher in order to increase the interfacial strength. In order to increase the interfacial strength, the holding pressure is preferably 5 MPa or more, and more preferably 10 MPa or more.
Retaining the holding pressure for a long time, for example, 5 seconds or longer, preferably 10 seconds or longer, more preferably the time until the mold temperature becomes equal to or lower than the melting point of the thermoplastic resin composition is from the viewpoint of increasing the interfacial strength. preferable.
[射出成形用の樹脂]
ハイブリッド成形体を製造するために用いる射出成形用の熱可塑性樹脂組成物としては、一般の射出成形に使用される熱可塑性樹脂組成物であれば特に限定されない。
熱可塑性樹脂組成物としては、以下に限定されるものではないが、例えば、ポリエチレン、ポリプロピレン、ポリ塩化ビニル、アクリル樹脂、スチレン系樹脂、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリアリレート、ポリフェニレンエーテル、変性ポリフェニレンエーテル樹脂、全芳香族ポリエステル、ポリアセタール、ポリカーボネート、ポリエーテルイミド、ポリエーテルサルフォン、ポリアミド系樹脂、ポリサルフォン、ポリエーテルエーテルケトン、ポリエーテルケトン等の一種又は二種以上を混合した樹脂組成物が挙げられる。
また、これらの熱可塑性樹脂組成物には、各種充填材が配合されていてもよい。
各種充填材としては、強化繊維と同種の材料の不連続強化材料である短繊維、長繊維材料等が挙げられる。
不連続強化材料にガラス短繊維、長繊維を用いる場合、本実施形態の連続繊維強化樹脂成形体を構成する連続強化繊維に塗布される集束剤と同様のもの用いてもよい。
サイジング剤(集束剤)は、(シラン)カップリング剤、潤滑剤、及び結束剤からなることが好ましい。(シラン)カップリング剤、潤滑剤、結束剤の種類に関しては、前述の連続強化繊維の集束剤と同様のものが使用できる。[Resin for injection molding]
The thermoplastic resin composition for injection molding used for producing a hybrid molded product is not particularly limited as long as it is a thermoplastic resin composition used for general injection molding.
The thermoplastic resin composition is not limited to the following, but is not limited to, for example, polyethylene, polypropylene, polyvinyl chloride, acrylic resin, styrene resin, polyethylene terephthalate, polybutylene terephthalate, polyarylate, polyphenylene ether, and modified polyphenylene. Examples thereof include a resin composition obtained by mixing one or more of ether resin, total aromatic polyester, polyacetal, polycarbonate, polyetherimide, polyethersulfone, polyamide resin, polysulfone, polyetheretherketone, polyetherketone and the like. Be done.
Further, various fillers may be blended in these thermoplastic resin compositions.
Examples of various fillers include short fibers and long fiber materials, which are discontinuous reinforcing materials of the same type as the reinforcing fibers.
When glass staple fibers and long fibers are used as the discontinuous reinforcing material, the same as the sizing agent applied to the continuous reinforcing fibers constituting the continuous fiber reinforced resin molded body of the present embodiment may be used.
The sizing agent (focusing agent) is preferably composed of a (silane) coupling agent, a lubricant, and a binding agent. As for the types of the (silane) coupling agent, the lubricant, and the binding agent, the same ones as those of the above-mentioned continuous reinforcing fiber sizing agent can be used.
射出成形に用いる熱可塑性樹脂組成物は、連続繊維強化樹脂成形体と射出成形した熱可塑性樹脂組成物部分との界面強度の観点から、連続繊維強化樹脂成形体を構成する熱可塑性樹脂と類似のものが好ましく、同種類のものがより好ましい。具体的には、連続繊維強化樹脂成形体を構成する熱可塑性樹脂にポリアミド66を用いた場合には、射出成形用の熱可塑性樹脂組成物の樹脂材料は、ポリアミド66が好ましい。
その他として、基材を金型に設置してダブルベルトプレス機により圧縮する成形方法や、設置した基材の四方を囲むように型枠を設置し、ダブルベルトプレス機により加圧し成形する方法や、一つ又は複数の温度に設定した加熱用の圧縮成型機と、一つ又は複数の温度に設定した冷却用の圧縮成型機を用意し、基材を設置した金型を順番に、圧縮成型機に投入して成形する成形方法などが挙げられる。The thermoplastic resin composition used for injection molding is similar to the thermoplastic resin constituting the continuous fiber reinforced resin molded body from the viewpoint of the interface strength between the continuous fiber reinforced resin molded body and the injection molded thermoplastic resin composition portion. Those of the same type are preferable, and those of the same type are more preferable. Specifically, when polyamide 66 is used as the thermoplastic resin constituting the continuous fiber reinforced resin molded body, polyamide 66 is preferable as the resin material of the thermoplastic resin composition for injection molding.
Other methods include a molding method in which the base material is installed in a mold and compressed by a double belt press machine, and a method in which a mold is installed so as to surround the four sides of the installed base material and pressed by a double belt press machine for molding. Prepare a compression molding machine for heating set to one or more temperatures and a compression molding machine for cooling set to one or more temperatures, and compress mold the molds on which the base materials are installed in order. Examples thereof include a molding method in which the product is put into a machine and molded.
[連続繊維強化樹脂成形体の樹脂含浸率]
図2に示すように、連続繊維強化樹脂成形体における熱可塑性樹脂の含浸率は、連続繊維強化樹脂成形体の断面における、空隙の割合により求める。具体的には連続繊維強化樹脂成形体を任意の位置で切断し、エポキシ樹脂等に包埋、研磨した後に光学顕微鏡観察を行うことで得られた画像を、解析ソフトにより画像解析することによって計算する。
図6に示すように、含浸率(%)とは、所定面積を100%としたとき、以下の式:
含浸率(%)={1-(空隙面積/連続強化繊維束面積)}×100
で計算される。本実施形態の連続繊維強化樹脂成形体の含浸率は、強度、外観の観点から、98%以上が好ましく、99%以上がより好ましく、99.5%以上が更に好ましく、99.9%以上が最も好ましい。[Resin impregnation rate of continuous fiber reinforced resin molded product]
As shown in FIG. 2, the impregnation rate of the thermoplastic resin in the continuous fiber reinforced resin molded product is determined by the ratio of voids in the cross section of the continuous fiber reinforced resin molded product. Specifically, the image obtained by cutting the continuous fiber reinforced resin molded body at an arbitrary position, embedding it in an epoxy resin or the like, polishing it, and then observing it with an optical microscope is calculated by image analysis using analysis software. do.
As shown in FIG. 6, the impregnation rate (%) is the following formula when a predetermined area is 100%.
Impregnation rate (%) = {1- (void area / continuous reinforcing fiber bundle area)} x 100
It is calculated by. From the viewpoint of strength and appearance, the impregnation rate of the continuous fiber reinforced resin molded product of the present embodiment is preferably 98% or more, more preferably 99% or more, further preferably 99.5% or more, and 99.9% or more. Most preferred.
[連続強化繊維]
連続強化繊維は通常の連続繊維強化樹脂成形体に使用されるものであることができる。
連続強化繊維としては、以下に限定されるものではないが、例えば、ガラス繊維、炭素繊維、植物繊維、アラミド繊維、超高強力ポリエチレン繊維、ポリベンザゾール系繊維、液晶ポリエステル繊維、ポリケトン繊維、金属繊維、セラミックス繊維等が挙げられる。
機械的特性、熱的特性、汎用性の観点から、ガラス繊維、炭素繊維、植物繊維、アラミド繊維が好ましく、生産性の面からは、ガラス繊維が好ましい。
連続強化繊維として、ガラス繊維を選択する場合、集束剤を用いてもよく、サイジング剤(集束剤)は、シランカップリング剤、潤滑剤、及び結束剤からなることが好ましく、連続強化繊維の周りを被膜する樹脂と強い結合を作る集束剤であることにより、空隙率の少ない連続繊維強化樹脂成形体を得ることができ、合成樹脂として熱可塑性樹脂を用いる場合には、集束剤は熱可塑性樹脂用の集束剤であることが好ましい。熱可塑性樹脂用の集束剤とは、連続強化繊維を電気炉で30℃/minで300℃まで昇温し、室温に戻した際に連続強化繊維の剛性が、加熱前の連続強化繊維の剛性よりも大きくならない物を指す。熱可塑性樹脂用の集束剤とは、例えば、ポリアミド樹脂を合成樹脂として選択する場合、シランカップリング剤として、ポリアミド樹脂の末端基であるカルボキシル基とアミノ基と結合しやすいものを選択する必要がある。具体的には例えば、γ-アミノプロピルトリメトキシシランやエポキシシランが挙げられる。
結束剤としてはポリアミド樹脂と濡れ性のよい、又は表面張力の近い樹脂を用いる必要がある。具体的には、例えば、ポリウレタン樹脂のエマルジョンやポリアミド樹脂のエマルジョンやその変性体を選択することができる。潤滑剤としてはシランカップリング剤と結束剤を阻害しないものを用いる必要があり、例えば、カルナウバワックスが挙げられる。[Continuous reinforcement fiber]
The continuous reinforcing fiber can be one used in a normal continuous fiber reinforced resin molded body.
The continuous reinforcing fiber is not limited to the following, and is, for example, glass fiber, carbon fiber, plant fiber, aramid fiber, ultra-high strength polyethylene fiber, polybenzazole fiber, liquid crystal polyester fiber, polyketone fiber, metal. Examples include fibers and ceramic fibers.
From the viewpoint of mechanical properties, thermal properties, and versatility, glass fiber, carbon fiber, plant fiber, and aramid fiber are preferable, and from the viewpoint of productivity, glass fiber is preferable.
When glass fiber is selected as the continuous reinforcing fiber, a sizing agent may be used, and the sizing agent (binding agent) is preferably composed of a silane coupling agent, a lubricant, and a binding agent, and is around the continuous reinforcing fiber. By being a sizing agent that forms a strong bond with the resin that coats the resin, a continuous fiber reinforced resin molded body with a small void ratio can be obtained, and when a thermoplastic resin is used as the synthetic resin, the sizing agent is a thermoplastic resin. It is preferable that it is a sizing agent for. The sizing agent for thermoplastic resin is the rigidity of the continuous reinforcing fiber when the temperature of the continuous reinforcing fiber is raised to 300 ° C at 30 ° C / min in an electric furnace and the temperature is returned to room temperature, and the rigidity of the continuous reinforcing fiber before heating. Refers to something that does not grow larger than. As the sizing agent for a thermoplastic resin, for example, when a polyamide resin is selected as a synthetic resin, it is necessary to select a silane coupling agent that easily binds to a carboxyl group and an amino group, which are terminal groups of the polyamide resin. be. Specific examples thereof include γ-aminopropyltrimethoxysilane and epoxysilane.
As the binding agent, it is necessary to use a resin having good wettability with a polyamide resin or having a surface tension close to that of the polyamide resin. Specifically, for example, an emulsion of a polyurethane resin, an emulsion of a polyamide resin, or a modified product thereof can be selected. As the lubricant, it is necessary to use a lubricant that does not inhibit the silane coupling agent and the binding agent, and examples thereof include carnauba wax.
集束剤は加熱プレス中に熱可塑性樹脂中に50%以上が拡散することが熱可塑性樹脂の連続強化繊維への含浸性の観点から好ましく、70%以上であることがより好ましく、80%以上であることが更に好ましく、90%以上であることが最も好ましい。集束剤の拡散は成形品を、良溶媒によりマトリックス樹脂を溶解させ、残った強化繊維を、XPS測定を行う等で求めることができ、マトリックス樹脂がポリアミドの場合、HFIPやフェノールを用いることが好ましい。
集束剤が加熱プレス中に熱可塑性樹脂中に90%以上拡散し、かつ、熱可塑性樹脂の末端官能基の内、カップリング剤と反応性がある末端基が、加熱プレス前後で減少しているとき、カップリング剤と熱可塑性樹脂の末端官能基が結合している。
連続強化繊維には、カップリング剤と熱可塑性樹脂の末端官能基との反応を促進させる触媒が塗布されていてもよく、かかる触媒としては、例えば、連続強化繊維としてガラス繊維を、熱可塑性樹脂としてポリアミド樹脂を選択する場合、シランカップリング剤が有するアミノ基とポリアミド樹脂の末端基であるカルボキシル基との結合反応を促進させる、次亜リン酸ナトリウム等のリン酸類が挙げられる。It is preferable that 50% or more of the sizing agent diffuses into the thermoplastic resin during the heating press from the viewpoint of impregnation of the thermoplastic resin into the continuously reinforcing fibers, more preferably 70% or more, and more preferably 80% or more. It is more preferably present, and most preferably 90% or more. Diffusion of the sizing agent can be obtained by dissolving the matrix resin in the molded product with a good solvent and measuring the remaining reinforcing fibers by XPS measurement or the like. When the matrix resin is polyamide, it is preferable to use HFIP or phenol. ..
The sizing agent diffuses 90% or more into the thermoplastic resin during the heating press, and among the terminal functional groups of the thermoplastic resin, the terminal groups reactive with the coupling agent are reduced before and after the heating press. At that time, the coupling agent and the terminal functional group of the thermoplastic resin are bonded.
The continuous reinforcing fiber may be coated with a catalyst that promotes the reaction between the coupling agent and the terminal functional group of the thermoplastic resin, and the catalyst may be, for example, glass fiber as the continuous reinforcing fiber and the thermoplastic resin. When a polyamide resin is selected, examples thereof include phosphoric acids such as sodium hypophosphite which promote the bonding reaction between the amino group of the silane coupling agent and the carboxyl group which is the terminal group of the polyamide resin.
[シランカップリング剤]
シランカップリング剤は、通常、ガラス繊維の表面処理剤として用いられ、界面接着強度向上に寄与する。
シランカップリング剤としては、以下に限定されるものではないが、例えば、γ-アミノプロピルトリメトキシシラン、N-β-(アミノエチル)-γ-アミノプロピルメチルジメトキシシラン等のアミノシラン類;γ-メルカプトプロピルトリメトキシシラン及びγ-メルカプトプロピルトリエトキシシラン等のメルカプトシラン類;エポキシシラン類;ビニルシラン類、マレイン酸類等が挙げられる。合成樹脂としてポリアミドを用いる際には、アミノシラン類やマレイン酸類が好ましく、合成樹脂としてエポキシ樹脂を用いる際にはエポキシシラン類が好ましい。[Silane coupling agent]
The silane coupling agent is usually used as a surface treatment agent for glass fibers and contributes to the improvement of interfacial adhesive strength.
The silane coupling agent is not limited to the following, but is, for example, aminosilanes such as γ-aminopropyltrimethoxysilane and N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane; γ- Examples thereof include mercaptosilanes such as mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane; epoxysilanes; vinylsilanes, maleic acids and the like. When polyamide is used as the synthetic resin, aminosilanes and maleic acids are preferable, and when epoxy resin is used as the synthetic resin, epoxysilanes are preferable.
[潤滑剤]
潤滑剤は、ガラス繊維の開繊性向上に寄与する。
潤滑剤としては、目的に応じた通常の液体又は固体の任意の潤滑材料が使用可能であり、以下に限定されるものではないが、例えば、カルナウバワックスやラノリンワックス等の動植物系又は鉱物系のワックス;脂肪酸アミド、脂肪酸エステル、脂肪酸エーテル、芳香族系エステル、芳香族系エーテル等の界面活性剤等が挙げられる。[lubricant]
The lubricant contributes to improving the openness of the glass fiber.
As the lubricant, any ordinary liquid or solid lubricating material depending on the purpose can be used, and the lubricant is not limited to the following, but is, for example, animal-plant or mineral-based such as carnauba wax and lanolin wax. Wax; Examples thereof include fatty acid amides, fatty acid esters, fatty acid ethers, aromatic esters, surfactants such as aromatic ethers, and the like.
[結束剤]
結束剤は、ガラス繊維の集束性向上及び界面接着強度向上に寄与する。
結束剤としては、目的に応じたポリマー、熱可塑性樹脂が使用可能である。
結束剤としてのポリマーは、以下に限定されるものではないが、例えば、アクリル酸のホモポリマー、アクリル酸とその他共重合性モノマーとのコポリマー、並びにこれらの第1級、第2級及び第3級アミンとの塩等が挙げられる。また、例えば、m-キシリレンジイソシアナート、4,4’-メチレンビス(シクロヘキシルイソシアナート)及びイソホロンジイソシアナート等のイソシアネートと、ポリエステル系やポリエーテル系のジオールとから合成されるポリウレタン系樹脂も好適に使用される。
アクリル酸のホモポリマーとしては、重量平均分子量1,000~90,000であることが好ましく、より好ましくは1,000~25,000である。
アクリル酸とその他共重合性モノマーとのコポリマーを構成する共重合性モノマーとしては、以下に限定されるものではないが、例えば、水酸基及び/又はカルボキシル基を有するモノマーのうち、アクリル酸、マレイン酸、メタクリル酸、ビニル酢酸、クロトン酸、イソクロトン酸、フマル酸、イタコン酸、シトラコン酸、及びメサコン酸よりなる群から選択される1種以上が挙げられる(但し、アクリル酸のみの場合を除く)。共重合性モノマーとして、エステル系モノマーを1種以上有することが好ましい。
アクリル酸のホモポリマー及びコポリマーの第1級、第2級及び第3級アミンとの塩としては、以下に限定されるものではないが、例えば、トリエチルアミン塩、トリエタノールアミン塩やグリシン塩等が挙げられる。中和度は、他の併用薬剤(シランカップリング剤等)との混合溶液の安定性向上や、アミン臭低減の観点から、20~90%とすることが好ましく、40~60%とすることがより好ましい。
塩を形成するアクリル酸のポリマーの重量平均分子量は、特に制限されないが、3,000~50,000の範囲が好ましい。ガラス繊維の集束性向上の観点から、3,000以上が好ましく、複合成形体とした際の特性向上の観点から50,000以下が好ましい。[Bundling agent]
The binding agent contributes to the improvement of the cohesiveness of the glass fiber and the improvement of the interfacial adhesive strength.
As the binding agent, a polymer or a thermoplastic resin suitable for the purpose can be used.
Polymers as binders are, but are not limited to, homopolymers of acrylic acid, copolymers of acrylic acid with other copolymerizable monomers, and their primary, secondary and tertiary. Examples include salts with grade amines. Further, for example, a polyurethane resin synthesized from isocyanates such as m-xylylene diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate) and isophoron diisocyanate and polyester-based or polyether-based diols is also suitable. Used for.
The weight average molecular weight of the acrylic acid homopolymer is preferably 1,000 to 90,000, more preferably 1,000 to 25,000.
The copolymerizable monomer constituting the copolymer of acrylic acid and other copolymerizable monomers is not limited to the following, and for example, among the monomers having a hydroxyl group and / or a carboxyl group, acrylic acid and maleic acid are used. , Methacrylic acid, vinyl acetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. It is preferable to have one or more ester-based monomers as the copolymerizable monomer.
The salt of the homopolymer of acrylic acid and the copolymer with the primary, secondary and tertiary amines is not limited to the following, and examples thereof include triethylamine salts, triethanolamine salts and glycine salts. Can be mentioned. The degree of neutralization is preferably 20 to 90%, preferably 40 to 60%, from the viewpoint of improving the stability of the mixed solution with other concomitant agents (silane coupling agent, etc.) and reducing the amine odor. Is more preferable.
The weight average molecular weight of the acrylic acid polymer forming the salt is not particularly limited, but is preferably in the range of 3,000 to 50,000. From the viewpoint of improving the focusing property of the glass fiber, 3,000 or more is preferable, and from the viewpoint of improving the characteristics when the composite molded body is formed, 50,000 or less is preferable.
結束剤として用いられる熱可塑性樹脂としては、以下に限定されるものではないが、例えば、ポリオレフィン系樹脂、ポリアミド系樹脂、ポリアセタール系樹脂、ポリカーボネート系樹脂、ポリエステル系樹脂、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリエーテルスルフォン、ポリフェニレンサルファイド、熱可塑性ポリエーテルイミド、熱可塑性フッ素系樹脂、及びこれらを変性させた変性熱可塑性樹脂等が挙げられる。結束剤として用いられる熱可塑性樹脂は、連続強化繊維の周囲を被覆する樹脂と同種の熱可塑性樹脂及び/又は変性熱可塑性樹脂であると、複合成形体となった後、ガラス繊維と熱可塑性樹脂の接着性が向上し、好ましい。 The thermoplastic resin used as a binder is not limited to the following, but is not limited to, for example, a polyolefin resin, a polyamide resin, a polyacetal resin, a polycarbonate resin, a polyester resin, a polyether ketone, and a polyether ether. Examples thereof include ketones, polyether sulfone, polyphenylene sulfide, thermoplastic polyetherimide, thermoplastic fluororesins, and modified thermoplastic resins obtained by modifying them. If the thermoplastic resin used as the binding agent is a thermoplastic resin and / or a modified thermoplastic resin of the same type as the resin that covers the periphery of the continuous reinforcing fiber, it becomes a composite molded body, and then the glass fiber and the thermoplastic resin. The adhesiveness of the resin is improved, which is preferable.
更に、一層、連続強化繊維とそれを被覆する熱可塑性樹脂の接着性を向上させ、集束剤を水分散体としてガラス繊維に付着させる場合において、乳化剤成分の比率を低減、あるいは乳化剤不要とできる等の観点から、結束剤として用いられる熱可塑性樹脂としては、変性熱可塑性樹脂が好ましい。
ここで、変性熱可塑性樹脂とは、熱可塑性樹脂の主鎖を形成し得るモノマー成分以外に、その熱可塑性樹脂の性状を変化させる目的で、異なるモノマー成分を共重合させ、親水性、結晶性、熱力学特性等を改質したものを意味する。
結束剤として用いられる変性熱可塑性樹脂は、以下に限定されるものではないが、例えば、変性ポリオレフィン系樹脂、変性ポリアミド系樹脂、変性ポリエステル系樹脂等が挙げられる。
結束剤としての変性ポリオレフィン系樹脂とは、エチレン、プロピレン等のオレフィン系モノマーと不飽和カルボン酸等のオレフィン系モノマーと共重合可能なモノマーとの共重合体であり、公知の方法で製造できる。オレフィン系モノマーと不飽和カルボン酸とを共重合させたランダム共重合体でもよいし、オレフィンに不飽和カルボン酸をグラフトしたグラフト共重合体でもよい。Further, the adhesiveness between the continuous reinforcing fiber and the thermoplastic resin covering the continuous reinforcing fiber can be further improved, and when the sizing agent is attached to the glass fiber as an aqueous dispersion, the ratio of the emulsifier component can be reduced or the emulsifier can be eliminated. From the viewpoint of the above, the modified thermoplastic resin is preferable as the thermoplastic resin used as the binding agent.
Here, the modified thermoplastic resin is copolymerized with different monomer components for the purpose of changing the properties of the thermoplastic resin in addition to the monomer components that can form the main chain of the thermoplastic resin, and is hydrophilic and crystalline. , Means modified thermodynamic properties, etc.
The modified thermoplastic resin used as a binding agent is not limited to the following, and examples thereof include modified polyolefin-based resins, modified polyamide-based resins, and modified polyester-based resins.
The modified polyolefin-based resin as a binder is a copolymer of an olefin-based monomer such as ethylene and propylene and a monomer copolymerizable with an olefin-based monomer such as unsaturated carboxylic acid, and can be produced by a known method. It may be a random copolymer obtained by copolymerizing an olefin-based monomer and an unsaturated carboxylic acid, or a graft copolymer obtained by grafting an unsaturated carboxylic acid onto an olefin.
オレフィン系モノマーとしては、以下に限定されるものではないが、例えば、エチレン、プロピレン、1-ブテン等が挙げられる。これらは1種のみを単独で使用してもよく、あるいは2種以上を組み合わせて使用してもよい。オレフィン系モノマーと共重合可能なモノマーとしては、例えば、アクリル酸、マレイン酸、無水マレイン酸、メタクリル酸、ビニル酢酸、クロトン酸、イソクロトン酸、フマル酸、イタコン酸、シトラコン酸、メサコン酸等の不飽和カルボン酸等が挙げられ、これらは、1種のみを単独で使用してもよく、2種以上を組み合わせて使用してもよい。
オレフィン系モノマーと、当該オレフィン系モノマーと共重合可能なモノマーとの共重合比率としては、共重合の合計質量を100質量%として、オレフィン系モノマー60~95質量%、オレフィン系モノマーと共重合可能なモノマー5~40質量%であることが好ましく、オレフィン系モノマー70~85質量%、オレフィン系モノマーと共重合可能なモノマー15~30質量%であることがより好ましい。オレフィン系モノマーが60質量%以上であれば、マトリックスとの親和性が良好であり、また、オレフィン系モノマーの質量%が95質量%以下であれば、変性ポリオレフィン系樹脂の水分散性が良好で、連続強化繊維への均一付与が行いやすい。Examples of the olefin-based monomer include, but are not limited to, ethylene, propylene, and 1-butene. These may be used alone or in combination of two or more. Examples of the monomer copolymerizable with the olefin-based monomer include acrylic acid, maleic acid, maleic anhydride, methacrylic acid, vinylacetic acid, crotonic acid, isocrotonic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. Examples thereof include saturated carboxylic acids, and these may be used alone or in combination of two or more.
As the copolymerization ratio of the olefin-based monomer and the monomer copolymerizable with the olefin-based monomer, the total mass of the copolymerization is 100% by mass, and the olefin-based monomer is 60 to 95% by mass, and the olefin-based monomer can be copolymerized with the olefin-based monomer. The content is preferably 5 to 40% by mass, more preferably 70 to 85% by mass of the olefin-based monomer, and more preferably 15 to 30% by mass of the monomer copolymerizable with the olefin-based monomer. When the olefin-based monomer is 60% by mass or more, the affinity with the matrix is good, and when the mass% of the olefin-based monomer is 95% by mass or less, the water dispersibility of the modified polyolefin-based resin is good. , It is easy to uniformly apply to continuous reinforcing fibers.
結束剤として用いられる変性ポリオレフィン系樹脂は、共重合により導入したカルボキシル基等の変性基が、塩基性化合物で中和されていてもよい。塩基性化合物としては、以下に限定されるものではないが、例えば、水酸化ナトリウム、水酸化カリウム等のアルカリ類;アンモニア;モノエタノールアミン、ジエタノールアミン等のアミン類が挙げられる。結束剤として用いられる変性ポリオレフィン系樹脂の重量平均分子量は、特に制限されないが、5,000~200,000が好ましく、50,000~150,000がより好ましい。ガラス繊維の集束性向上の観点から5,000以上が好ましく、水分散性とする場合の乳化安定性の観点から200,000以下が好ましい。 In the modified polyolefin resin used as a binding agent, a modifying group such as a carboxyl group introduced by copolymerization may be neutralized with a basic compound. Examples of the basic compound include, but are not limited to, alkalis such as sodium hydroxide and potassium hydroxide; ammonia; amines such as monoethanolamine and diethanolamine. The weight average molecular weight of the modified polyolefin resin used as the binding agent is not particularly limited, but is preferably 5,000 to 200,000, more preferably 50,000 to 150,000. From the viewpoint of improving the cohesiveness of the glass fiber, 5,000 or more is preferable, and from the viewpoint of emulsification stability in the case of water dispersibility, 200,000 or less is preferable.
結束剤として用いられる変性ポリアミド系樹脂とは、分子鎖中にポリアルキレンオキサイド鎖や3級アミン成分等の親水基を導入した変性ポリアミド化合物であり、公知の方法で製造できる。
分子鎖中にポリアルキレンオキサイド鎖を導入する場合は、例えば、ポリエチレングリコールやポリプロピレングリコール等の一部又は全部をジアミン又はジカルボン酸に変性したものを共重合して製造される。3級アミン成分を導入する場合は、例えばアミノエチルピペラジン、ビスアミノプロピルピペラジン、α-ジメチルアミノε-カプロラクタム等を共重合して製造される。The modified polyamide resin used as a binding agent is a modified polyamide compound in which a hydrophilic group such as a polyalkylene oxide chain or a tertiary amine component is introduced into a molecular chain, and can be produced by a known method.
When a polyalkylene oxide chain is introduced into a molecular chain, it is produced by copolymerizing, for example, a part or all of polyethylene glycol, polypropylene glycol or the like modified with diamine or dicarboxylic acid. When a tertiary amine component is introduced, it is produced by copolymerizing, for example, aminoethylpiperazine, bisaminopropylpiperazine, α-dimethylaminoε-caprolactam and the like.
結束剤として用いられる変性ポリエステル系樹脂とは、ポリカルボン酸又はその無水物とポリオールとの共重合体で、かつ末端を含む分子骨格中に親水基を有する樹脂であり、公知の方法で製造できる。
親水基としては、例えば、ポリアルキレンオキサイド基、スルホン酸塩、カルボキシル基、これらの中和塩等が挙げられる。ポリカルボン酸又はその無水物としては、芳香族ジカルボン酸、スルホン酸塩含有芳香族ジカルボン酸、脂肪族ジカルボン酸、脂環式ジカルボン酸、3官能以上のポリカルボン酸等が挙げられる。
芳香族ジカルボン酸としては、以下に限定されるものではないが、例えば、フタル酸、テレフタル酸、イソフタル酸、オルトフタル酸、1,5-ナフタレンジカルボン酸、2,6-ナフタレンジカルボン酸、無水フタル酸等が挙げられる。
スルホン酸塩含有芳香族ジカルボン酸としては、以下に限定されるものではないが、例えば、スルホテレフタル酸塩、5-スルホイソフタル酸塩、5-スルホオルトフタル酸塩等が挙げられる。
脂肪族ジカルボン酸又は脂環式ジカルボン酸としては、以下に限定されるものではないが、例えば、フマル酸、マレイン酸、イタコン酸、コハク酸、アジピン酸、アゼライン酸、セバシン酸、ダイマー酸、1,4-シクロヘキサンジカルボン酸、無水コハク酸、無水マレイン酸等が挙げられる。
3官能以上のポリカルボン酸としては、以下に限定されるものではないが、例えば、トリメリット酸、ピロメリット酸、無水トリメリット酸、無水ピロメリット酸等が挙げられる。
これらの中で、変性ポリエステル系樹脂の耐熱性を向上させる観点から、全ポリカルボン酸成分の40~99モル%が芳香族ジカルボン酸であることが好ましい。また、変性ポリエステル系樹脂を水分散液とする場合の乳化安定性の観点から、全ポリカルボン酸成分の1~10モル%がスルホン酸塩含有芳香族ジカルボン酸であることが好ましい。The modified polyester resin used as a binder is a copolymer of a polycarboxylic acid or its anhydride and a polyol, and has a hydrophilic group in the molecular skeleton including the terminal, and can be produced by a known method. ..
Examples of the hydrophilic group include a polyalkylene oxide group, a sulfonate, a carboxyl group, and a neutralizing salt thereof. Examples of the polycarboxylic acid or its anhydride include aromatic dicarboxylic acids, sulfonate-containing aromatic dicarboxylic acids, aliphatic dicarboxylic acids, alicyclic dicarboxylic acids, and trifunctional or higher functional polycarboxylic acids.
The aromatic dicarboxylic acid is not limited to the following, but is not limited to, for example, phthalic acid, terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and phthalic anhydride. And so on.
Examples of the sulfonate-containing aromatic dicarboxylic acid include, but are not limited to, sulfoterephthalate, 5-sulfoisophthalate, and 5-sulfoortophthalate.
The aliphatic dicarboxylic acid or the alicyclic dicarboxylic acid is not limited to the following, and is, for example, fumaric acid, maleic acid, itaconic acid, succinic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, 1 , 4-Cyclohexanedicarboxylic acid, succinic acid anhydride, maleic acid anhydride and the like can be mentioned.
Examples of the trifunctional or higher functional polycarboxylic acid include, but are not limited to, trimellitic acid, pyromellitic acid, trimellitic anhydride, pyromellitic anhydride and the like.
Among these, from the viewpoint of improving the heat resistance of the modified polyester resin, it is preferable that 40 to 99 mol% of the total polycarboxylic acid component is an aromatic dicarboxylic acid. Further, from the viewpoint of emulsion stability when the modified polyester resin is used as an aqueous dispersion, it is preferable that 1 to 10 mol% of the total polycarboxylic acid component is a sulfonate-containing aromatic dicarboxylic acid.
変性ポリエステル系樹脂を構成するポリオールとしては、ジオール、3官能以上のポリオール等が挙げられる。
ジオールとしては、以下に限定されるものではないが、例えば、エチレングリコール、ジエチレングリコール、ポリエチレングリコール、プロピレングリコール、ポリプロピレングリコール、ポリブチレングリコール、1,3-プロパンジオール、1,4-ブタンジオール、1,6-ヘキサンジオール、ネオペンチルグリコール、ポリテトラメチレングリコール、1,4-シクロヘキサンジオール、1,4-シクロヘキサンジメタノール、ビスフェノールA又はそのアルキレンオキサイド付加物等が挙げられる。3官能以上のポリオールとしては、トリメチロールプロパン、グリセリン、ペンタエリスリトール等が挙げられる。Examples of the polyol constituting the modified polyester resin include diols and trifunctional or higher functional polyols.
The diol is not limited to the following, but is not limited to, for example, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polybutylene glycol, 1,3-propanediol, 1,4-butanediol, 1, Examples thereof include 6-hexanediol, neopentyl glycol, polytetramethylene glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, bisphenol A or an alkylene oxide adduct thereof. Examples of the trifunctional or higher functional polyol include trimethylolpropane, glycerin, and pentaerythritol.
変性ポリエステル系樹脂を構成するポリカルボン酸又はその無水物とポリオールとの共重合比率としては、共重合成分の合計質量を100質量%として、ポリカルボン酸又はその無水物40~60質量%、ポリオール40~60質量%であることが好ましく、ポリカルボン酸又はその無水物45~55質量%、ポリオール45~55質量%がより好ましい。
変性ポリエステル系樹脂の重量平均分子量としては、3,000~100,000が好ましく、10,000~30,000がより好ましい。ガラス繊維の集束性向上の観点から3,000以上が好ましく、水分散性とする場合の乳化安定性の観点から100,000以下が好ましい。As the copolymerization ratio of the polycarboxylic acid or its anhydride constituting the modified polyester resin and the polyol, the total mass of the copolymerized components is 100% by mass, and the polycarboxylic acid or its anhydride is 40 to 60% by mass, the polyol. It is preferably 40 to 60% by mass, more preferably 45 to 55% by mass of the polycarboxylic acid or its anhydride, and more preferably 45 to 55% by mass of the polyol.
The weight average molecular weight of the modified polyester resin is preferably 3,000 to 100,000, more preferably 10,000 to 30,000. From the viewpoint of improving the focusing property of the glass fiber, 3,000 or more is preferable, and from the viewpoint of emulsification stability in the case of water dispersibility, 100,000 or less is preferable.
結束剤として用いる、ポリマー、熱可塑性樹脂は、1種のみを単独で用いてもよいし、2種類以上を併用してもよい。
結束剤の全量を100質量%として、アクリル酸のホモポリマー、アクリル酸とその他共重合性モノマーとのコポリマー、並びにこれらの第1級、第2級及び第3級アミンとの塩より選択された1種以上のポリマーを50質量%以上、60質量%以上用いることがより好ましい。As the polymer and the thermoplastic resin used as the binding agent, only one kind may be used alone, or two or more kinds may be used in combination.
Selected from homopolymers of acrylic acid, copolymers of acrylic acid with other copolymerizable monomers, and salts with these primary, secondary and tertiary amines, with the total amount of binder as 100% by mass. It is more preferable to use 50% by mass or more and 60% by mass or more of one or more kinds of polymers.
[ガラス繊維用の集束剤の組成]
連続強化繊維としてガラス繊維を用いる場合、当該ガラス繊維の集束剤においては、それぞれ、シランカップリング剤を0.1~2質量%、潤滑剤を0.01~1質量%、結束剤を1~25質量%を含有することが好ましく、これらの成分を水で希釈し、全質量を100質量%に調整することが好ましい。
ガラス繊維用の集束剤におけるシランカップリング剤の配合量は、ガラス繊維の集束性向上及び界面接着強度向上と複合成形体の機械的強度向上との観点から、0.1~2質量%が好ましく、より好ましくは0.1~1質量%、更に好ましくは0.2~0.5質量%である。[Composition of sizing agent for glass fiber]
When glass fiber is used as the continuous reinforcing fiber, the silane coupling agent is 0.1 to 2% by mass, the lubricant is 0.01 to 1% by mass, and the binding agent is 1 to 1, respectively, in the sizing agent for the glass fiber. It is preferable to contain 25% by mass, and it is preferable to dilute these components with water to adjust the total mass to 100% by mass.
The blending amount of the silane coupling agent in the sizing agent for glass fibers is preferably 0.1 to 2% by mass from the viewpoint of improving the sizing property of the glass fibers, improving the interfacial adhesive strength, and improving the mechanical strength of the composite molded body. , More preferably 0.1 to 1% by mass, still more preferably 0.2 to 0.5% by mass.
ガラス繊維用の集束剤における潤滑剤の配合量は、充分な潤滑性を与えるという観点から、好ましくは0.01質量%以上、より好ましくは0.02質量%以上であり、界面接着強度向上と複合成形体の機械的強度向上の観点から、好ましくは1質量%以下、より好ましくは0.5質量%以下である。
ガラス繊維用の集束剤における結束剤の配合量は、ガラス繊維の集束性制御及び界面接着強度向上と複合成形体の機械的強度向上との観点から、好ましくは1~25質量%、より好ましくは3~15質量%、更に好ましくは3~10質量%である。The blending amount of the lubricant in the sizing agent for glass fiber is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and improves the interfacial adhesive strength, from the viewpoint of providing sufficient lubricity. From the viewpoint of improving the mechanical strength of the composite molded body, it is preferably 1% by mass or less, more preferably 0.5% by mass or less.
The blending amount of the binding agent in the sizing agent for glass fibers is preferably 1 to 25% by mass, more preferably 1 to 25% by mass, from the viewpoint of controlling the sizing property of the glass fibers, improving the interfacial adhesive strength, and improving the mechanical strength of the composite molded body. It is 3 to 15% by mass, more preferably 3 to 10% by mass.
[ガラス繊維用の集束剤の使用態様]
ガラス繊維用の集束剤は、使用態様に応じて、水溶液、コロイダルディスパージョンの形態、乳化剤を用いたエマルジョンの形態等、いずれの形態に調整してもよいが、集束剤の分散安定性向上、耐熱性向上の観点から、水溶液の形態とすることが好ましい。
本実施形態連続繊維強化樹脂成形体構成する連続強化繊維としてのガラス繊維は、上述した集束剤を、公知のガラス繊維の製造工程において、ローラー型アプリケーター等の公知の方法を用いて、ガラス繊維に付与して製造したガラス繊維を乾燥することによって連続的に得られる。
集束剤は、ガラス繊維100質量%に対し、シランカップリング剤、潤滑剤及び結束剤の合計質量として、好ましくは0.1~3質量%、より好ましくは0.2~2質量%、更に好ましくは0.2~1質量%付与する。
ガラス繊維の集束性制御と界面接着強度向上の観点から、集束剤の付与量が、ガラス繊維100質量%に対し、シランカップリング剤、潤滑剤及び結束剤の合計質量として0.1質量%以上であることが好ましく、糸の取扱い性の観点から3質量%以下であることが好ましい。[Usage of sizing agent for glass fiber]
The sizing agent for glass fibers may be adjusted to any form such as an aqueous solution, a form of colloidal dispersion, or an emulsion using an emulsifier, depending on the mode of use, but the dispersion stability of the sizing agent is improved. From the viewpoint of improving heat resistance, it is preferable to use an aqueous solution.
In the present embodiment, the glass fiber as the continuous reinforcing fiber constituting the continuous fiber reinforced resin molded body is made into a glass fiber by using the above-mentioned sizing agent in a known method such as a roller type applicator in a known glass fiber manufacturing process. It is continuously obtained by drying the glass fibers produced by applying the fibers.
The sizing agent is preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, still more preferably 0.2 to 2% by mass, as the total mass of the silane coupling agent, the lubricant and the binding agent with respect to 100% by mass of the glass fiber. Is given in an amount of 0.2 to 1% by mass.
From the viewpoint of controlling the sizing property of the glass fiber and improving the interfacial adhesive strength, the amount of the sizing agent applied is 0.1% by mass or more as the total mass of the silane coupling agent, the lubricant and the binding agent with respect to 100% by mass of the glass fiber. It is preferable that the amount is 3% by mass or less from the viewpoint of handleability of the yarn.
尚、連続強化繊維として、炭素繊維を選択した場合には、集束剤は、カップリング剤、潤滑剤、結束剤からなることが好ましい。集束剤、潤滑剤、結束剤の種類については、特に制限はなく公知の物が使用できる。具体的材料としては、特開2015-101794号公報に記載されている材料を使用できる。カップリング剤としては炭素繊維の表面に存在する水酸基と相性の良いもの、結束剤としては選択した合成樹脂と、濡れ性が良いものや表面張力の近いもの、潤滑剤としてはカップリング剤と結束剤を阻害しないものを選択することができる。 When carbon fiber is selected as the continuous reinforcing fiber, the bundling agent is preferably composed of a coupling agent, a lubricant, and a bundling agent. The types of the sizing agent, the lubricant, and the sizing agent are not particularly limited, and known substances can be used. As a specific material, the material described in Japanese Patent Application Laid-Open No. 2015-101794 can be used. As a coupling agent, one having good compatibility with the hydroxyl group existing on the surface of the carbon fiber, as a binding agent, one having good wettability or having a similar surface tension with the selected synthetic resin, and as a lubricant, one binding with a coupling agent. Those that do not inhibit the agent can be selected.
その他の連続強化繊維を用いる場合、連続強化繊維の特性に応じ、ガラス繊維、炭素繊維に用いる集束剤の種類、付与量を適宜選択すればよく、炭素繊維に用いる集束剤に準じた集束剤の種類、付与量とすることが好ましい。 When other continuous reinforcing fibers are used, the type and amount of the sizing agent used for the glass fiber and the carbon fiber may be appropriately selected according to the characteristics of the continuous reinforced fiber, and the sizing agent similar to the sizing agent used for the carbon fibers may be used. It is preferable to use the type and the amount to be imparted.
[連続強化繊維の形状]
連続強化繊維は複数本の強化繊維からなるマルチフィラメントであり、単糸数は、取扱い性の観点から30~15,000本であることが好ましい。連続強化繊維の単糸径は、強度の観点、及び、取り扱い性の観点から2~30μmであることが好ましく、4~25μmであることがより好ましく、6~20μmであることが更に好ましく、8~18μmであることが最も好ましい。
連続強化繊維の単糸径R(μm)と密度D(g/cm3)の積RDは、複合糸の取り扱い性と成形体の強度の観点から、好ましくは5~100μm・g/cm3、より好ましくは10~50μm・g/cm3、更に好ましくは15~45μm・g/cm3、より更に好ましくは20~45μm・g/cm3である。[Shape of continuous reinforcing fiber]
The continuous reinforcing fiber is a multifilament composed of a plurality of reinforcing fibers, and the number of single yarns is preferably 30 to 15,000 from the viewpoint of handleability. The single yarn diameter of the continuous reinforcing fiber is preferably 2 to 30 μm, more preferably 4 to 25 μm, further preferably 6 to 20 μm, and even more preferably 6 to 20 μm from the viewpoint of strength and handleability. Most preferably, it is ~ 18 μm.
The product RD of the single yarn diameter R (μm) and the density D (g / cm 3 ) of the continuous reinforcing fiber is preferably 5 to 100 μm · g / cm 3 from the viewpoint of handleability of the composite yarn and the strength of the molded body. It is more preferably 10 to 50 μm · g / cm 3 , still more preferably 15 to 45 μm · g / cm 3 , and even more preferably 20 to 45 μm · g / cm 3 .
密度Dは比重計により測定することができる。他方、単糸径(μm)は、密度(g/cm3)と繊度(dtex)、単糸数(本)から、以下の式:
連続強化繊維の積RDを所定の範囲とするには、市販で入手可能な連続強化繊維について、連続強化繊維の有する密度に応じて、繊度(dtex)及び単糸数(本)を適宜選択すればよい。例えば、連続強化繊維としてガラス繊維を用いる場合、密度が約2.5g/cm3であるから、単糸径が2~40μmのものを選べばよい。具体的には、ガラス繊維の単糸径が9μmである場合、繊度660dtexで単糸数400本のガラス繊維を選択することにより、積RDは、23となる。また、ガラス繊維の単糸径が17μmである場合、繊度11,500dtexで単糸数2,000本のガラス繊維を選択することにより、積RDは、43となる。連続強化繊維として炭素繊維を用いる場合、密度が約1.8g/cm3であるから、単糸径が2.8~55μmのものを選べばよい。具体的には、炭素繊維の単糸径が7μmである場合、繊度2,000dtexで単糸数3,000本の炭素繊維を選択することにより、積RDは、13となる。連続強化繊維としてアラミド繊維を用いる場合、密度が約1.45g/cm3であるから、単糸径が3.4~68μmのものを選べばよい。具体的には、アラミド繊維の単糸径が12μmである場合、繊度1,670dtexで単糸数1,000本のアラミド繊維を選択することにより、積RDは、17となる。
連続強化繊維、例えば、ガラス繊維は、原料ガラスを計量、混合し、溶融炉で溶融ガラスとし、これを紡糸してガラスフィラメントとし、集束剤を塗布し、紡糸機を経て、ダイレクトワインドロービング(DWR)、ケーキ、撚りを入れたヤーン等の巻き取り形態として製造される。連続強化繊維はどのような形態でも構わないが、ヤーン、ケーキ、DWRに巻き取ってあると、樹脂を被覆させる工程での生産性、生産安定性が高まるため好ましい。生産性の観点からはDWRが最も好ましい。In order to keep the product RD of the continuous reinforcing fibers within a predetermined range, the fineness (dtex) and the number of single yarns (lines) of the commercially available continuous reinforcing fibers should be appropriately selected according to the density of the continuous reinforcing fibers. good. For example, when glass fiber is used as the continuous reinforcing fiber, the density is about 2.5 g / cm 3 , so that a single yarn diameter of 2 to 40 μm may be selected. Specifically, when the single yarn diameter of the glass fiber is 9 μm, the product RD becomes 23 by selecting the glass fiber having a fineness of 660 dtex and the number of single yarns of 400. When the single yarn diameter of the glass fiber is 17 μm, the product RD becomes 43 by selecting the glass fiber having a fineness of 11,500 dtex and the number of single yarns of 2,000. When carbon fiber is used as the continuous reinforcing fiber, the density is about 1.8 g / cm 3 , so that the single yarn diameter of 2.8 to 55 μm may be selected. Specifically, when the single yarn diameter of the carbon fiber is 7 μm, the product RD becomes 13 by selecting the carbon fiber having a fineness of 2,000 dtex and the number of single yarns of 3,000. When aramid fiber is used as the continuous reinforcing fiber, the density is about 1.45 g / cm 3 , so that the single yarn diameter of 3.4 to 68 μm may be selected. Specifically, when the single yarn diameter of the aramid fiber is 12 μm, the product RD becomes 17 by selecting the aramid fiber having a fineness of 1,670 dtex and the number of single yarns of 1,000.
For continuously reinforced fiber, for example, glass fiber, raw glass is weighed and mixed to make molten glass in a melting furnace, which is spun into a glass filament, coated with a sizing agent, passed through a spinning machine, and then subjected to direct winding roving (DWR). ), Cakes, twisted yarns, etc. are manufactured as a winding form. The continuous reinforcing fiber may be in any form, but it is preferable that the continuous reinforcing fiber is wound around a yarn, a cake, or a DWR because the productivity and production stability in the process of coating the resin are improved. From the viewpoint of productivity, DWR is the most preferable.
[合成樹脂]
本実施形態の連続繊維強化樹脂成形体のマトリックス樹脂を構成する合成樹脂は熱可塑性樹脂でも熱硬化性樹脂でも構わないが、成形サイクルの観点、リサイクル性の観点から、熱可塑性樹脂が好ましい。[Synthetic resin]
The synthetic resin constituting the matrix resin of the continuous fiber reinforced resin molded body of the present embodiment may be a thermoplastic resin or a thermosetting resin, but a thermoplastic resin is preferable from the viewpoint of the molding cycle and recyclability.
[熱可塑性樹脂]
本実施形態の連続繊維強化樹脂成形体を構成する熱可塑性樹脂は1種類のみを用いてもよいし、複数種を併用しても構わない。連続繊維強化樹脂との接着性の観点から2種類以上の熱可塑性樹脂を含んでいることが好ましい。2種類以上の熱可塑性樹脂を含んでいる場合は、連続強化繊維の長さ方向に直交する断面における連続強化繊維1本と合成樹脂との間の極界面において、該連続強化繊維の周縁部から、該連続強化繊維1本の半径の10分の1離れた周縁外側領域において、2種類以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂以外の樹脂の占有割合が、該樹脂領域の全体として占有割合が最も高い樹脂の占有割合よりも高いことが、生産性と強化繊維と樹脂の界面強度の観点から好ましい。
熱可塑性樹脂は、吸水率が0.1重量%以上であることがカップリング剤と熱可塑性樹脂の末端官能基との反応性の観点から好ましく、0.3重量%以上であることがより好ましく、0.5重量%以上であることがより好ましく、0.8重量%以上であることが更に好ましく、1.0重量%以上であることが更に好ましく、1.5重量%以上であることが最も好ましい。熱可塑性樹脂の吸水率はカールフィッシャー水分計等を用いて、測定することができる。
熱可塑性樹脂には、カップリング剤と、熱可塑性樹脂の末端官能基との反応を促進させる触媒が添加されていると好ましく、かかる触媒としては、例えば、連続強化繊維としてガラス繊維、熱可塑性樹脂としてポリアミド樹脂を選択する場合、シランカップリング剤が有するアミノ基とポリアミド樹脂の末端基であるカルボキシル基との間の結合反応を促進させる、次亜リン酸ナトリウム等のリン酸類が挙げられる。[Thermoplastic resin]
Only one type of thermoplastic resin constituting the continuous fiber reinforced resin molded product of the present embodiment may be used, or a plurality of types may be used in combination. From the viewpoint of adhesiveness to the continuous fiber reinforced resin, it is preferable to contain two or more types of thermoplastic resins. When two or more kinds of thermoplastic resins are contained, at the polar interface between one continuous reinforcing fiber and the synthetic resin in a cross section orthogonal to the length direction of the continuous reinforcing fiber, from the peripheral portion of the continuous reinforcing fiber. In the outer peripheral region 1/10 of the radius of the continuous reinforcing fiber, the occupancy ratio of the resin other than the resin having the highest occupancy ratio as a whole of the resin region among the two or more types of thermoplastic resins is It is preferable that the occupancy ratio of the resin region as a whole is higher than the occupancy ratio of the resin having the highest occupancy ratio from the viewpoint of productivity and the interface strength between the reinforcing fiber and the resin.
The thermoplastic resin preferably has a water absorption rate of 0.1% by weight or more from the viewpoint of reactivity between the coupling agent and the terminal functional group of the thermoplastic resin, and more preferably 0.3% by weight or more. , 0.5% by weight or more, more preferably 0.8% by weight or more, further preferably 1.0% by weight or more, and more preferably 1.5% by weight or more. Most preferred. The water absorption rate of the thermoplastic resin can be measured using a Karl Fischer titer or the like.
It is preferable that a catalyst that promotes the reaction between the coupling agent and the terminal functional group of the thermoplastic resin is added to the thermoplastic resin, and examples of such a catalyst include glass fiber as a continuous reinforcing fiber and a thermoplastic resin. When a polyamide resin is selected as the above, examples thereof include phosphoric acids such as sodium hypophosphite which promote the bonding reaction between the amino group of the silane coupling agent and the carboxyl group which is the terminal group of the polyamide resin.
熱可塑性樹脂に含まれる粒子状添加材の含有量は30ppm以下であることが、連続繊維強化樹脂複合材料の機械強度の観点から好ましく、20ppm以下であるとより好ましく、10ppm以下であると更に好ましく、5ppm以下であると最も好ましい。
熱可塑性樹脂に含まれる粒子状添加材としては、例えば、カーボンブラック等が挙げられる。The content of the particulate additive contained in the thermoplastic resin is preferably 30 ppm or less from the viewpoint of the mechanical strength of the continuous fiber reinforced resin composite material, more preferably 20 ppm or less, still more preferably 10 ppm or less. Most preferably, it is 5 ppm or less.
Examples of the particulate additive contained in the thermoplastic resin include carbon black and the like.
[μドロップ生成係数]
μドロップ生成係数は樹脂と強化繊維の相性を示す指標であり、μドロップ生成係数は樹脂の主成分のみでなく、樹脂に含まれる微量成分も影響する。熱可塑性樹脂は、強化繊維とのμドロップ生成係数が10以上(タッチ回数が4の場合)であることが好ましい。μドロップ生成係数は、例えば、複合材界面特性評価装置(HM410、東栄産業株式会社)を用いて、強化繊維の単糸1本に樹脂付けをする際に、強化繊維に樹脂を複数回タッチさせ、生成したμドロップの数を数え、下記式:
(μドロップ生成係数)={(生成したμドロップ数)/(強化繊維に樹脂をタッチさせた回数)}×10
により算出できる。[Μ drop generation coefficient]
The μ-drop formation coefficient is an index showing the compatibility between the resin and the reinforcing fiber, and the μ-drop formation coefficient affects not only the main component of the resin but also the trace components contained in the resin. The thermoplastic resin preferably has a μ drop generation coefficient of 10 or more (when the number of touches is 4) with the reinforcing fiber. The μ drop generation coefficient is determined by, for example, using a composite material interface characteristic evaluation device (HM410, Toei Sangyo Co., Ltd.) to apply resin to one single yarn of reinforcing fiber by touching the reinforcing fiber multiple times. , Count the number of μ drops generated, the following formula:
(Μ drop generation coefficient) = {(number of generated μ drops) / (number of times the resin is touched on the reinforcing fiber)} × 10
Can be calculated by
[2種以上の熱可塑性樹脂]
本実施形態の連続繊維強化樹脂成形体のマトリックス樹脂を構成する熱可塑性樹脂は2種類以上であってもよい。2種類以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)が、2種類以上の熱可塑性樹脂の合計の占有面積の内、85%~99%であることが好ましく、2種類以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)融点が最も高い樹脂であると耐熱性の観点から好ましい。
2種類以上の熱可塑性樹脂の内、融点が最も高い樹脂の融点と融点が最も低い樹脂の融点との差は、35℃以上であることが好ましく、より好ましくは100℃以上である。連続繊維強化樹脂成形体に含まれる熱可塑性樹脂の種類は、連続繊維強化樹脂成形体の断面をレーザーラマン顕微鏡で解析することにより特定でき、各熱可塑性樹脂の融点及びガラス転移温度は、樹脂の組成から示差走査熱量計(DSC)により算出することができる。また、熱可塑性樹脂の混合物の融点は、熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)の融点と同じであると、耐熱性の観点から好ましい。[Two or more types of thermoplastic resin]
The thermoplastic resin constituting the matrix resin of the continuous fiber reinforced resin molded product of the present embodiment may be two or more types. Of the two or more types of thermoplastic resin, the resin (main resin) that occupies the highest proportion of the entire resin region is 85% to 99% of the total occupied area of the two or more types of thermoplastic resin. Of the two or more types of thermoplastic resins, the resin having the highest occupancy ratio in the entire resin region (main resin) and the resin having the highest melting point is preferable from the viewpoint of heat resistance.
Of the two or more types of thermoplastic resins, the difference between the melting point of the resin having the highest melting point and the melting point of the resin having the lowest melting point is preferably 35 ° C. or higher, more preferably 100 ° C. or higher. The type of thermoplastic resin contained in the continuous fiber reinforced resin molded body can be identified by analyzing the cross section of the continuous fiber reinforced resin molded body with a laser Raman microscope, and the melting point and glass transition temperature of each thermoplastic resin are determined by the resin. It can be calculated from the composition by a differential scanning calorimeter (DSC). Further, it is preferable that the melting point of the mixture of the thermoplastic resin is the same as the melting point of the resin (main resin) having the highest occupancy ratio in the entire resin region among the thermoplastic resins from the viewpoint of heat resistance.
本実施形態の連続繊維強化樹脂成形体を構成する2種以上の熱可塑性樹脂混合物の昇温融解ピーク温度と降温結晶化ピーク温度との差は、該2種以上の熱可塑性樹脂を構成する樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)の昇温融解ピーク温度と降温結晶化ピーク温度との差よりも小さいと、成形性と含浸速度のバランスに優れるため好ましい。昇温融解ピーク温度と降温結晶化ピーク温度はDSCにより算出することができる。 The difference between the temperature-increasing peak temperature and the temperature-decreasing crystallization peak temperature of the two or more types of thermoplastic resin mixture constituting the continuous fiber-reinforced resin molded body of the present embodiment is the resin constituting the two or more types of thermoplastic resin. Of these, if it is smaller than the difference between the temperature-increasing and melting peak temperature and the temperature-decreasing crystallization peak temperature of the resin (main resin) having the highest occupancy ratio as a whole of the resin region, it is preferable because the balance between moldability and impregnation rate is excellent. The rising melting peak temperature and the lowering crystallization peak temperature can be calculated by DSC.
本実施形態の連続繊維強化樹脂成形体を構成する2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)と連続強化繊維との間の結合力よりも、該樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)以外の少なくとも一つの樹脂(副樹脂)と前記連続強化繊維との間の結合力が大きいことが、含浸性と強度の観点から好ましい。各熱可塑性樹脂と連続強化繊維との間の結合力は、ナノインデンターを用いたプッシュアウト試験によって求めることができる。 Of the two or more types of thermoplastic resins constituting the continuous fiber reinforced resin molded body of the present embodiment, the bonding force between the resin (main resin) having the highest occupancy ratio as a whole in the resin region and the continuous reinforced fiber From the viewpoint of impregnation property and strength, the strong bonding force between the continuous reinforcing fiber and at least one resin (secondary resin) other than the resin (main resin) having the highest occupancy ratio as a whole in the resin region is large. preferable. The bond strength between each thermoplastic resin and the continuous reinforcing fiber can be determined by a pushout test using a nanoindenter.
本実施形態の連続繊維強化樹脂成形体を構成する2種以上熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)と連続強化繊維との間の表面張力の差よりも、該樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)以外の少なくとも一つの樹脂(副樹脂)と前記連続強化繊維との間の表面張力の差が小さいことが、含浸性と強度の観点から好ましい。また、本実施形態の連続繊維強化樹脂成形体を構成する2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)の連続強化繊維に対する濡れ性よりも、該樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)以外の少なくとも一つの樹脂(副樹脂)の、連続強化繊維に対する濡れ性が大きいことが、含浸性と強度の観点から好ましい。各熱可塑性樹脂と連続強化繊維との間の表面張力の差、濡れ性は、ホットプレート上で溶融した熱可塑性樹脂に連続強化繊維1本を埋め込み、連続強化繊維を引き抜いた際に、熱可塑性樹脂が連続繊維に引っ張られる長さによって評価することができる。 From the difference in surface tension between the resin (main resin) that occupies the highest proportion of the entire resin region and the continuous reinforcing fiber among the two or more types of thermoplastic resins constituting the continuous fiber reinforced resin molded body of the present embodiment. However, the impregnation property and strength are such that the difference in surface tension between the continuous reinforcing fiber and at least one resin (secondary resin) other than the resin (main resin) having the highest occupancy ratio as a whole in the resin region is small. It is preferable from the viewpoint of. Further, among the two or more types of thermoplastic resins constituting the continuous fiber reinforced resin molded body of the present embodiment, the wettability of the resin (main resin) having the highest occupancy ratio in the entire resin region to the continuous reinforced fibers is higher. It is preferable from the viewpoint of impregnation property and strength that at least one resin (secondary resin) other than the resin (main resin) having the highest occupancy ratio as a whole of the resin region has a high wettability with respect to the continuous reinforcing fiber. The difference in surface tension and wettability between each thermoplastic resin and the continuous reinforcing fiber is the thermoplasticity when one continuous reinforcing fiber is embedded in the thermoplastic resin melted on the hot plate and the continuous reinforcing fiber is pulled out. It can be evaluated by the length that the resin is pulled by the continuous fiber.
本実施形態の連続繊維強化樹脂成形体を構成する2種以上の熱可塑性樹脂の混合物の溶融粘度は、該2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)の溶融粘度と同じであるであると、強度と含浸性のバランスに優れることから好ましい。樹脂の溶融粘度はツインキャピラリーレオメーター等を用いて測定することができる。
本実施形態の連続繊維強化樹脂成形体を構成する2種以上の熱可塑性樹脂は、中間材の形態に応じてプレコンパウンドして用いてもよいし、ドライブレンドで中間材の樹脂形態を形成してもよい。The melt viscosity of the mixture of two or more types of thermoplastic resins constituting the continuous fiber reinforced resin molded body of the present embodiment is the resin having the highest occupancy ratio in the entire resin region among the two or more types of thermoplastic resins ( When the melt viscosity is the same as that of the main resin), it is preferable because the balance between strength and impregnation property is excellent. The melt viscosity of the resin can be measured using a twin capillary leometer or the like.
Two or more kinds of thermoplastic resins constituting the continuous fiber reinforced resin molded product of the present embodiment may be used by precompounding according to the form of the intermediate material, or the resin form of the intermediate material is formed by dry blending. You may.
[熱可塑性樹脂の形態]
熱可塑性樹脂の形態としては特に制限はないが、例えば、フィルム、ペレット、繊維、板、粉状、強化繊維にコーティングされたもの等が挙げられる。[Form of thermoplastic resin]
The form of the thermoplastic resin is not particularly limited, and examples thereof include films, pellets, fibers, plates, powders, and those coated with reinforcing fibers.
[1種又は2種以上の熱可塑性樹脂の種類]
熱可塑性樹脂は、以下に限定されるものではないが、例えば、ポリエチレン、ポリプロピレン等のポリオレフィン系樹脂;ポリアミド6、ポリアミド66、ポリアミド46等のポリアミド系樹脂;ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリトリメチレンテレフタレート等のポリエステル系樹脂;ポリオキシメチレン等のポリアセタール系樹脂;ポリカーボネート系樹脂;ポリエーテルケトン、ポリエーテルエーテルケトン、ポリエーテルグリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコール等のポリエーテル系樹脂;ポリエーテルスルフォン;ポリフェニレンサルファイド;熱可塑性ポリエーテルイミド;テトラフルオロエチレン-エチレン共重合体等の熱可塑性フッ素系樹脂;ポリウレタン系樹脂;アクリル系樹脂及びこれらを変性させた変性熱可塑性樹脂が挙げられる。[Type of one or more types of thermoplastic resin]
The thermoplastic resin is not limited to the following, but is, for example, a polyolefin resin such as polyethylene and polypropylene; a polyamide resin such as polyamide 6, polyamide 66 and polyamide 46; polyethylene terephthalate, polybutylene terephthalate and polytrimethylene. Polyester resin such as terephthalate; Polyacetal resin such as polyoxymethylene; Polycarbonate resin; Polyether resin such as polyether ketone, polyether ether ketone, polyether glycol, polypropylene glycol, polytetramethylene ether glycol; polyether Examples thereof include sulfone; polyphenylene sulfide; thermoplastic polyetherimide; thermoplastic fluororesin such as tetrafluoroethylene-ethylene copolymer; polyurethane resin; acrylic resin and modified thermoplastic resin obtained by modifying them.
これらの熱可塑性樹脂の中でも、ポリオレフィン系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、ポリエーテル系樹脂、ポリエーテルスルフォン、ポリフェニレンサルファイド、熱可塑性ポリエーテルイミド、熱可塑性フッ素系樹脂が好ましく、ポリオレフィン系樹脂、変性ポリオレフィン系樹脂、ポリアミド系樹脂、ポリエステル系樹脂、ポリウレタン系樹脂及びアクリル系樹脂が、機械的物性、汎用性の観点からより好ましく、熱的物性の観点を加えるとポリアミド系樹脂及びポリエステル系樹脂が更に好ましい。また、繰り返し荷重負荷に対する耐久性の観点からポリアミド系樹脂がより更に好ましい。 Among these thermoplastic resins, polyolefin resins, polyamide resins, polyester resins, polyether resins, polyether sulfone, polyphenylene sulfide, thermoplastic polyetherimide, and thermoplastic fluororesins are preferable, and polyolefin resins, Modified polyolefin resins, polyamide resins, polyester resins, polyurethane resins and acrylic resins are more preferable from the viewpoint of mechanical properties and versatility, and polyamide resins and polyester resins are more preferable from the viewpoint of thermal properties. More preferred. Further, a polyamide resin is more preferable from the viewpoint of durability against repeated load.
[ポリエステル系樹脂]
ポリエステル系樹脂とは、主鎖に-CO-O-(エステル)結合を有する高分子化合物を意味する。
ポリエステル系樹脂としては、以下に限定されるものではないが、例えば、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリテトラメチレンテレフタレート、ポリ-1,4-シクロヘキシレンジメチレンテレフタレート、ポリエチレン-2,6-ナフタレンジカルボキシレート等が挙げられる。
ポリエステル系樹脂は、ホモポリエステルであってもよく、また、共重合ポリエステルであってもよい。
共重合ポリエステルの場合、ホモポリエステルに適宜第3成分を共重合させたものが好ましく、第3成分としては、以下に限定されるものではないが、例えば、ジエチレングリコール、ネオペンチルグリコール、ポリアルキレングリコール等のジオール成分、アジピン酸、セバシン酸、フタル酸、イソフタル酸、5-ナトリウムスルホイソフタル酸等のジカルボン酸成分等が挙げられる。
また、バイオマス資源由来の原料を用いたポリエステル系樹脂を用いることもでき、以下に限定されるものではないが、例えば、ポリ乳酸、ポリブチレンスクシネート、ポリブチレンスクシネートアジペート等の脂肪族ポリエステル系樹脂、ポリブチレンアジペートテレフタレート等の芳香族ポリエステル系樹脂等が挙げられる。[Polyester resin]
The polyester resin means a polymer compound having an —CO—O— (ester) bond in the main chain.
The polyester resin is not limited to the following, but is not limited to, for example, polyethylene terephthalate, polybutylene terephthalate, polytetramethylene terephthalate, poly-1,4-cyclohexylene methylene terephthalate, polyethylene-2,6-naphthalene. Examples thereof include carboxylate.
The polyester-based resin may be a homopolyester or a copolymerized polyester.
In the case of the copolymerized polyester, it is preferable that the homopolyester is appropriately copolymerized with the third component, and the third component is not limited to the following, but is, for example, diethylene glycol, neopentyl glycol, polyalkylene glycol and the like. Examples thereof include a diol component, adicarboxylic acid component such as adipic acid, sebacic acid, phthalic acid, isophthalic acid, and 5-sodium sulfoisophthalic acid.
Further, a polyester-based resin using a raw material derived from a biomass resource can also be used, and is not limited to the following, and is, for example, an aliphatic such as polylactic acid, polybutylene succinate, and polybutylene succinate adipate. Examples thereof include polyester-based resins and aromatic polyester-based resins such as polybutylene adipate terephthalate.
[ポリアミド系樹脂]
ポリアミド系樹脂とは、主鎖に-CO-NH-(アミド)結合を有する高分子化合物を意味する。例えば、脂肪族系ポリアミド、芳香族系ポリアミド、全芳香族系ポリアミド等があげられるが、強化繊維との親和性の観点が高く強化繊維による補強効果が得られやすいという観点から脂肪族系ポリアミドが好ましい。
ポリアミド樹脂に含まれるカルボキシル末端基の量は、65μmol/g以上であることが樹脂と強化繊維の接着の観点から好ましく、70μmol/g以上であることがより好ましく、75μmol/g以上であることが更に好ましく、80μmol/g以上であることがより更に好ましい。
ポリアミド樹脂に含まれるアミノ末端基の量は、40μmol/g以下であることが樹脂と強化繊維の接着の観点から好ましく、35μmol/g以下であることがより好ましく、30μmol/g以下であることが更に好ましく、25μmol/g以下であることがより更に好ましい。
ポリアミド系樹脂としては、以下に限定されるものではないが、例えば、ラクタムの開環重合で得られるポリアミド、ω-アミノカルボン酸の自己縮合で得られるポリアミド、ジアミン及びジカルボン酸を縮合することで得られるポリアミド、並びにこれらの共重合体が挙げられる。
ポリアミド系樹脂は、1種を単独で用いてもよく、2種以上の混合物として用いてもよい。
ラクタムとしては、以下に限定されるものではないが、例えば、ピロリドン、カプロラクタム、ウンデカンラクタムやドデカラクタムが挙げられる。ω-アミノカルボン酸としては、以下に限定されるものではないが、例えば、ラクタムの水による開環化合物であるω-アミノ脂肪酸が挙げられる。ラクタム又はω-アミノカルボン酸はそれぞれ2種以上の単量体を併用して縮合させてもよい。[Polyamide resin]
The polyamide-based resin means a polymer compound having a -CO-NH- (amide) bond in the main chain. Examples thereof include aliphatic polyamides, aromatic polyamides, and all-aromatic polyamides. Aliphatic polyamides have a high affinity with reinforcing fibers and the reinforcing effect of the reinforcing fibers can be easily obtained. preferable.
The amount of the carboxyl-terminal group contained in the polyamide resin is preferably 65 μmol / g or more, more preferably 70 μmol / g or more, and more preferably 75 μmol / g or more, from the viewpoint of adhesion between the resin and the reinforcing fiber. It is more preferably 80 μmol / g or more, and even more preferably 80 μmol / g or more.
The amount of the amino-terminal group contained in the polyamide resin is preferably 40 μmol / g or less, more preferably 35 μmol / g or less, and more preferably 30 μmol / g or less, from the viewpoint of adhesion between the resin and the reinforcing fiber. It is more preferably 25 μmol / g or less, and even more preferably 25 μmol / g or less.
The polyamide-based resin is not limited to the following, but is, for example, by condensing a polyamide obtained by ring-opening polymerization of lactam, a polyamide obtained by self-condensation of ω-aminocarboxylic acid, a diamine and a dicarboxylic acid. Examples thereof include the obtained polyamides and copolymers thereof.
The polyamide resin may be used alone or as a mixture of two or more.
Examples of lactam include, but are not limited to, pyrrolidone, caprolactam, undecane lactam, and dodecalactam. Examples of the ω-aminocarboxylic acid include, but are not limited to, ω-amino fatty acid, which is a ring-opening compound of lactam with water. Lactam or ω-aminocarboxylic acid may be condensed by using two or more kinds of monomers in combination.
ジアミン(単量体)としては、以下に限定されるものではないが、例えば、ヘキサメチレンジアミンやペンタメチレンジアミン等の直鎖状の脂肪族ジアミン;2-メチルペンタンジアミンや2-エチルヘキサメチレンジアミン等の分岐型の脂肪族ジアミン;p-フェニレンジアミンやm-フェニレンジアミン等の芳香族ジアミン;シクロヘキサンジアミン、シクロペンタンジアミンやシクロオクタンジアミン等の脂環式ジアミンが挙げられる。
ジカルボン酸(単量体)としては、以下に限定されるものではないが、例えば、アジピン酸、ピメリン酸やセバシン酸等の脂肪族ジカルボン酸;フタル酸やイソフタル酸等の芳香族ジカルボン酸;シクロヘキサンジカルボン酸等の脂環式ジカルボン酸が挙げられる。単量体としてのジアミン及びジカルボン酸はそれぞれ1種単独又は2種以上の併用により縮合させてもよい。The diamine (monomer) is not limited to the following, but is, for example, a linear aliphatic diamine such as hexamethylenediamine or pentamethylenediamine; 2-methylpentanediamine or 2-ethylhexamethylenediamine. Such as branched aliphatic diamines; aromatic diamines such as p-phenylenediamine and m-phenylenediamine; alicyclic diamines such as cyclohexanediamine, cyclopentanediamine and cyclooctanediamine can be mentioned.
The dicarboxylic acid (monomer) is not limited to the following, but is, for example, an aliphatic dicarboxylic acid such as adipic acid, pimelic acid or sebacic acid; an aromatic dicarboxylic acid such as phthalic acid or isophthalic acid; cyclohexane. Examples thereof include alicyclic dicarboxylic acids such as dicarboxylic acids. Diamine and dicarboxylic acid as monomers may be condensed by one kind alone or two or more kinds in combination, respectively.
ポリアミド系樹脂としては、以下に限定されるものではないが、例えば、ポリアミド4(ポリα-ピロリドン)、ポリアミド6(ポリカプロアミド)、ポリアミド11(ポリウンデカンアミド)、ポリアミド12(ポリドデカンアミド)、ポリアミド46(ポリテトラメチレンアジパミド)、ポリアミド66(ポリヘキサメチレンアジパミド)、ポリアミド610、ポリアミド612、ポリアミド6T(ポリヘキサメチレンテレフタルアミド)、ポリアミド9T(ポリノナンメチレンテレフタルアミド)、及びポリアミド6I(ポリヘキサメチレンイソフタルアミド)、並びにこれらを構成成分として含む共重合ポリアミドが挙げられる。
共重合ポリアミドとしては、以下に限定されるものではないが、例えば、ヘキサメチレンアジパミド及びヘキサメチレンテレフタルアミドの共重合体、ヘキサメチレンアジパミド及びヘキサメチレンイソフタルアミドの共重合体、並びにヘキサメチレンテレフタルアミド及び2-メチルペンタンジアミンテレフタルアミドの共重合体が挙げられる。The polyamide-based resin is not limited to the following, but for example, polyamide 4 (poly α-pyrrolidone), polyamide 6 (polycaproamide), polyamide 11 (polyundecaneamide), and polyamide 12 (polydodecaneamide). , Polyamide 46 (Polytetramethylene adipamide), Polyamide 66 (Polyhexamethylene adipamide), Polyamide 610, Polyamide 612, Polyamide 6T (Polyhexamethylene terephthalamide), Polyamide 9T (Polynonan methylene terephthalamide), and Examples thereof include polyamide 6I (polyhexamethylene isophthalamide) and copolymerized polyamides containing these as constituents.
The copolymerized polyamide is not limited to the following, and is, for example, a copolymer of hexamethylene adipamide and hexamethylene terephthalamide, a copolymer of hexamethylene adipamide and hexamethylene isophthalamide, and hexa. Examples thereof include copolymers of methylene terephthalamide and 2-methylpentanediamine terephthalamide.
[連続繊維強化複合材料の賦形成形体の製造方法]
前記した方法により製造された連続繊維強化樹脂複合材料を、前記熱可塑性樹脂の融点以上にIRヒータ等により加熱し、金型等の型を用いてプレスし、その後、該熱可塑性樹脂の融点以下の温度まで冷却して、賦形する工程を含む方法により、連続繊維強化複合材料の賦形成形体を製造することができる。[Manufacturing method of formed form of continuous fiber reinforced composite material]
The continuous fiber reinforced resin composite material produced by the above method is heated above the melting point of the thermoplastic resin by an IR heater or the like, pressed using a mold such as a mold, and then below the melting point of the thermoplastic resin. By a method including a step of cooling to the temperature of the above and shaping, a formed form of a continuous fiber reinforced composite material can be produced.
[熱硬化性樹脂]
熱硬化性樹脂は、以下に限定されるものではないが、例えば、エポキシ樹脂、フェノール樹脂、メラミン樹脂、ユリア樹脂、不飽和ポリエステル樹脂などが挙げられる。これらの熱硬化性樹脂は1種を単独で又は2種類以上を組み合わせて用いることができる。[Thermosetting resin]
The thermosetting resin is not limited to the following, and examples thereof include epoxy resin, phenol resin, melamine resin, urea resin, and unsaturated polyester resin. These thermosetting resins can be used individually by 1 type or in combination of 2 or more types.
[本実施形態の連続繊維強化樹脂成形体(複合材料)の用途]
本実施形態の連続繊維強化樹脂成形体は、航空機、車、建設材料、ロボット、通信機器筐体等の構造材料用途に好適に使用することができる。
車用途においては、以下に限定されるものではないが、例えば、シャーシ/フレーム、足回り、駆動系部品、内装部品、外装部品、機能部品、その他部品に使用できる。
具体的には、ステアリング軸、マウント、サンルーフ、ステップ、スーフトリム、ドアトリム、トランク、ブートリッド、ボンネット、シートフレーム、シートバック、リトラクター、リタラクター支持ブラケット、クラッチ、ギア、プーリー、カム、アーゲー、弾性ビーム、バッフリング、ランプ、リフレクタ、グレージング、フロントエンドモジュール、バックドアインナー、ブレーキペダル、ハンドル、電装材、吸音材、ドア外装、内装パネル、インパネ、リアゲート、天井ハリ、シート、シート枠組み、ワイパー支柱、EPS(Electric Power Steering)、小型モーター、ヒートシンク、ECU(Engine Control Unit)ボックス、ECUハウジング、ステアリングギアボックスハウジング、プラスチックハウジング、EV(Electric Vehicle)モーター用筐体、ワイヤーハーネス、車載メーター、コンビネーションスイッチ、小型モーター、スプリング、ダンパー、ホイール、ホイールカバー、フレーム、サブフレーム、サイドフレーム、二輪フレーム、燃料タンク、オイルパン、インマニ、プロペラシャフト、駆動用モーター、モノコック、水素タンク、燃料電池の電極、パネル、フロアパネル、外板パネル、ドア、キャビン、ルーフ、フード、バルブ、EGR(Exhaust Gas Recirculation)バルブ、可変バルブタイミングユニット、コネクティングロッド、シリンダボア、メンバー(エンジンマウンティング、フロントフロアクロス、フットウェルクロス、シートクロス、インナーサイド、リヤクロス、サスペンション、ピラーリーンフォース、フロントサイド、フロントパネル、アッパー、ダッシュパネルクロス、ステアリング)、トンネル、締結インサート、クラッシュボックス、クラッシュレール、コルゲート、ルーフレール、アッパボディ、サイドレール、ブレーディング、ドアサラウンドアッセンブリー、エアバッグ用部材、ボディーピラー、ダッシュツゥピラーガセット、サスペンジョンタワー、バンパー、ボディーピラーロワー、フロントボディーピラー、レインフォースメント(インパネ、レール、ルーフ、フロントボディーピラー、ルーフレール、ルーフサイドレール、ロッカー、ドアベルトライン、フロントフロアアンダー、フロントボディーピラーアッパー、フロントボディーピラーロワー、センターピラー、センターピラーヒンジ、ドアアウトサイドパネル、)、サイドアウターパネル、フロントドアウインドゥフレーム、MICS(Minimum Intrusion Cabin System)バルク、トルクボックス、ラジエーターサポート、ラジエーターファン、ウォーターポンプ、燃料ポンプ、電子制御スロットルボディ、エンジン制御ECU、スターター、オルタネーター、マニホールド、トランスミッション、クラッチ、ダッシュパネル、ダッシュパネルインシュレータパッド、ドアサイドインパクトプロテクションビーム、バンパービーム、ドアビーム、バルクヘッド、アウタパッド、インナパッド、リヤシートロッド、ドアパネル、ドアトリムボドサブアッセンブリー、エネルギーアブソーバー(バンパー、衝撃吸収)、衝撃吸収体、衝撃吸収ガーニッシュ、ピラーガーニッシュ、ルーフサイドインナーガーニッシュ、樹脂リブ、サイドレールフロントスペーサー、サイドレールリアスペーサー、シートベルトプリテンショナー、エアバッグセンサー、アーム(サスペンション、ロアー、フードヒンジ)、サスペンションリンク、衝撃吸収ブラケット、フェンダーブラケット、インバーターブラケット、インバーターモジュール、フードインナーパネル、フードパネル、カウルルーバー、カウルトップアウターフロントパネル、カウルトップアウターパネル、フロアサイレンサー、ダンプシート、フードインシュレーター、フェンダーサイドパネルプロテクター、カウルインシュレーター、カウルトップベンチレータールーパー、シリンダーヘッドカバー、タイヤディフレクター、フェンダーサポート、ストラットタワーバー、ミッションセンタートンネル、フロアトンネル、ラジコアサポート、ラゲッジパネル、ラゲッジフロア、アクセルペダル、アクセルペダルベース等の部品として好適に使用することができる。[Use of continuous fiber reinforced resin molded product (composite material) of this embodiment]
The continuous fiber reinforced resin molded body of the present embodiment can be suitably used for structural material applications such as aircraft, cars, construction materials, robots, and communication equipment housings.
In vehicle applications, it can be used, for example, for chassis / frames, undercarriage, drive train parts, interior parts, exterior parts, functional parts, and other parts, but is not limited to the following.
Specifically, steering shafts, mounts, sun roofs, steps, souf trims, door trims, trunks, boot lids, bonnets, seat frames, seat backs, retractors, retractor support brackets, clutches, gears, pulleys, cams, argers, elastic beams. , Buff ring, lamp, reflector, glazing, front end module, back door inner, brake pedal, handle, electrical equipment, sound absorbing material, door exterior, interior panel, instrument panel, rear gate, ceiling tension, seat, seat frame, wiper support, EPS (Electric Power Steering), small motor, heat sink, ECU (Engine Control Unit) box, ECU housing, steering gearbox housing, plastic housing, EV (Electric Vehicle) motor housing, wire harness, in-vehicle meter, combination switch, Small motors, springs, dampers, wheels, wheel covers, frames, subframes, side frames, two-wheel frames, fuel tanks, oil pans, in-mani, propeller shafts, drive motors, monococks, hydrogen tanks, fuel cell electrodes, panels, Floor panels, exterior panels, doors, cabins, roofs, hoods, valves, EGR (Exhaust Gas Recirculation) valves, variable valve timing units, connecting rods, cylinder bores, members (engine mounting, front floor cloth, footwell cloth, seat cloth) , Inner side, rear cross, suspension, pillar lean force, front side, front panel, upper, dash panel cross, steering), tunnel, fastening insert, crash box, crash rail, corrugated, roof rail, upper body, side rail, braiding , Door surround assembly, air bag parts, body pillars, dash pillar gussets, suspension towers, bumpers, body pillar lowers, front body pillars, reinforcements (instrument panel, rails, roof, front body pillars, roof rails, roof side rails) , Rocker, door belt line, front floor under, front body pillar upper, front body pillar lower , Center pillar, center pillar hinge, door outside panel,), side outer panel, front door window frame, MICS (Minimum Intrusion Cabin System) bulk, torque box, radiator support, radiator fan, water pump, fuel pump, electronic control Throttle body, engine control ECU, starter, alternator, manifold, transmission, clutch, dash panel, dash panel insulator pad, door side impact protection beam, bumper beam, door beam, bulkhead, outer pad, inner pad, rear seat rod, door panel, door trim Bodo Sub Assembly, Energy Absorber (Bumper, Shock Absorber), Shock Absorber, Shock Absorber Garnish, Pillar Garnish, Roof Side Inner Garnish, Resin Rib, Side Rail Front Spacer, Side Rail Rear Spacer, Seatbelt Pretensioner, Airbag Sensor , Arm (suspension, lower, hood hinge), suspension link, shock absorbing bracket, fender bracket, inverter bracket, inverter module, hood inner panel, hood panel, cowl louver, cowl top outer front panel, cowl top outer panel, floor silencer , Dump sheet, hood insulator, fender side panel protector, cowl insulator, cowl top ventilator looper, cylinder head cover, tire deflector, fender support, strut tower bar, mission center tunnel, floor tunnel, radiator support, luggage panel, luggage floor, It can be suitably used as a component such as an accelerator pedal and an accelerator pedal base.
本実施形態の連続繊維強化樹脂成形体(複合材料)は、通信機器筐体用途においては、例えば、直方体状であってよい。
筐体の特性としては、電波透過性が要求させる部材であって、KEC法により測定される電界シールド性が周波数1GHz帯において、10dB未満であることが好ましく、より好ましくは5dB未満、さらに好ましくは、0.1dB未満である。本特性を有する連続強化繊維としては、連続強化ガラス繊維が用いることができる。
筺体の平均肉厚は、1mm以下が好ましく、0.5mm以下がさらに好ましく、0.4mm以下が最も好ましい。例えば、プレフォームを介して製造することにより、連続繊維の乱れが少なく、ボイドの発生がない、目的の厚みの筺体を製造することができる。The continuous fiber reinforced resin molded body (composite material) of the present embodiment may be, for example, a rectangular parallelepiped shape in a communication device housing application.
As a characteristic of the housing, it is a member required for radio wave transmission, and the electric field shielding property measured by the KEC method is preferably less than 10 dB in the frequency 1 GHz band, more preferably less than 5 dB, still more preferably. , Less than 0.1 dB. As the continuously reinforced fiber having this characteristic, a continuously reinforced glass fiber can be used.
The average wall thickness of the housing is preferably 1 mm or less, more preferably 0.5 mm or less, and most preferably 0.4 mm or less. For example, by manufacturing via preform, it is possible to manufacture a housing having a desired thickness with less disturbance of continuous fibers and no generation of voids.
以下、本発明を実施例、比較例により具体的に説明するが、本発明はこれらの実施例に限定されるものではなく、本発明の要旨の範囲内で種々変形して実施することができることはいうまでもない。 Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples, and can be variously modified and carried out within the scope of the gist of the present invention. Needless to say.
まず、実施例、比較例で用いた測定方法等について説明する。
[連続強化繊維1本の端から、連続強化繊維1本の半径の10分の1の領域の平均の空隙率]
連続繊維強化樹脂成形体をバンドソーにより切削し、切削した試験片を研磨機(小型精密試料作成システム IS-POLISHER ISPP-1000(株式会社池上精機))により、研磨面に400g/cm2の力がかかるように研磨した。研磨は耐水ペーパー番手#220で10分間、耐水ペーパー番手#400で2分間、耐水ペーパー番手#800で5分間、耐水ペーパー番手#1200で10分間、耐水ペーパー番手#2000で15分間、炭化ケイ素フィルム粒度9μmで15分間、アルミナフィルム粒度5μmで15分間、アルミナフィルム粒度3μmで15分間、アルミナフィルム粒度1μmで15分間、バフ研磨紙発泡ポリウレタンを用いた粒度0.1μmのコロイダルシリカ(バイカロックス0.1CR)で10分間の順番で行い、各研磨で約7mL/minで水を加えながら研磨した。研磨したサンプルをSEM(S-4700、株式会社日立ハイテクノロジーズ)により観察し、得られた画像から、連続強化繊維1本の半径の10分の1の領域の空隙率を算出した。任意に選択した連続強化繊維100本について観察を行い、連続強化繊維1本の半径の10分の1の領域の平均の空隙率と、空隙率が10%以下であるもの割合を求めた。First, the measurement methods and the like used in Examples and Comparative Examples will be described.
[Average porosity in the region of 1/10 of the radius of one continuous reinforcing fiber from the end of one continuous reinforcing fiber]
A continuous fiber reinforced resin molded body is cut with a band saw, and the cut test piece is subjected to a force of 400 g / cm 2 on the polished surface by a polishing machine (small precision sample preparation system IS-POLISHER ISPP-1000 (Ikegami Seiki Co., Ltd.)). Polished in this way. Polishing is performed with water-resistant paper count # 220 for 10 minutes, water-resistant paper count # 400 for 2 minutes, water-resistant paper count # 800 for 5 minutes, water-resistant paper count # 1200 for 10 minutes, water-resistant paper count # 2000 for 15 minutes, and silicon carbide film. Colloidal silica with a particle size of 0.1 μm using buffed abrasive paper foamed polyurethane for 15 minutes with a particle size of 9 μm, 15 minutes with an alumina film particle size of 5 μm, 15 minutes with an alumina film particle size of 3 μm, and 15 minutes with an alumina film particle size of 1 μm. It was carried out in the order of 1CR) for 10 minutes, and each polishing was performed while adding water at about 7 mL / min. The polished sample was observed by SEM (S-4700, Hitachi High-Technologies Corporation), and the void ratio in the region of 1/10 of the radius of one continuous reinforcing fiber was calculated from the obtained image. Observation was performed on 100 arbitrarily selected continuous reinforcing fibers, and the average porosity in the region of 1/10 of the radius of one continuous reinforcing fiber and the ratio of those having a porosity of 10% or less were determined.
[含浸率]
成形体の断面を切り出し、エポキシ樹脂に包埋し、連続強化繊維が破損しないように注意しながら研磨を行った。マイクロスコープにより観察し、得られた画像から、連続強化繊維束、合成樹脂、空隙のそれぞれの占有面積を求め、連続強化繊維束(全体)面積に対する空隙面積の割合を求め、以下の式:
含浸率(%)={1-(空隙面積/連続強化繊維束面積)}×100
により算出した。[Immersion rate]
A cross section of the molded product was cut out, embedded in epoxy resin, and polished while being careful not to damage the continuous reinforcing fibers. From the images obtained by observing with a microscope, the occupied areas of the continuous reinforcing fiber bundle, the synthetic resin, and the voids were obtained, and the ratio of the void area to the continuous reinforcing fiber bundle (total) area was obtained.
Impregnation rate (%) = {1- (void area / continuous reinforcing fiber bundle area)} x 100
Calculated by
[引張応力]
成形体から長さ70mm、幅10mm、肉厚2mmの短冊状の試験片を切り出し、インストロン万能試験機にて、試験片を、長手方向に30mmの間隔でチャッキングし、速度5mm/min、23℃50%RH環境下、及び150℃、50%の恒温槽内で引張応力(MPa)を測定した。[Tensile stress]
A strip-shaped test piece having a length of 70 mm, a width of 10 mm, and a wall thickness of 2 mm is cut out from the molded body, and the test pieces are chucked at intervals of 30 mm in the longitudinal direction with an Instron universal testing machine, and the speed is 5 mm / min. The tensile stress (MPa) was measured in a constant temperature bath at 23 ° C. and 50% RH and at 150 ° C. and 50%.
[曲げ応力、曲げ弾性率]
成形体から長さ100mm、幅10mm、肉厚2mmの短冊状の試験片を切り出し、インストロン万能試験機にて、3点曲げ用の治具を用い、スパン間を32mmに設定して速度1mm/min、23℃、50%RH環境下で曲げ応力(MPa)、曲げ弾性率(GPa)を測定した。[Bending stress, flexural modulus]
A strip-shaped test piece with a length of 100 mm, a width of 10 mm, and a wall thickness of 2 mm is cut out from the molded body, and a jig for 3-point bending is used with an Instron universal testing machine, the span interval is set to 32 mm, and the speed is 1 mm. Bending stress (MPa) and flexural modulus (GPa) were measured in a / min, 23 ° C., and 50% RH environment.
[連続繊維強化樹脂中の強化繊維の体積比率(Vf)の測定と成形中に漏れ出した樹脂量比率]
連続繊維強化樹脂成形体2gを切り出し、電気炉に入れ、温度650℃で3時間加熱して、樹脂を焼き飛ばした。その後、室温まで自然冷却し、残されたガラス繊維の質量を測定することで、連続繊維強化樹脂成形体に含まれるガラス繊維と樹脂の比率を求めた。また、求めた比率から、密度で割りかえすことにより、連続繊維強化樹脂成形体に対する強化繊維の体積比率(Vf)を求めた。また仕込みの樹脂量と成形後の連続繊維強化樹脂成形体に含まれる樹脂量から、成形中に漏れ出した樹脂量を求め、漏れ出した樹脂量を仕込みの樹脂量で割りかえすことで、漏れ出した樹脂量比率を求めた。[Measurement of volume ratio (Vf) of reinforcing fiber in continuous fiber reinforced resin and ratio of resin amount leaked during molding]
2 g of a continuous fiber reinforced resin molded product was cut out, placed in an electric furnace, and heated at a temperature of 650 ° C. for 3 hours to burn off the resin. Then, the glass fiber was naturally cooled to room temperature, and the mass of the remaining glass fiber was measured to determine the ratio of the glass fiber to the resin contained in the continuous fiber reinforced resin molded body. Further, the volume ratio (Vf) of the reinforced fiber to the continuous fiber reinforced resin molded body was obtained by dividing the obtained ratio by the density. Further, the amount of resin leaked during molding is obtained from the amount of resin charged and the amount of resin contained in the continuous fiber reinforced resin molded body after molding, and the leaked resin amount is divided by the amount of resin charged to cause leakage. The ratio of the amount of resin produced was calculated.
[2種以上の繊維強化樹脂内の各熱可塑性樹脂の種類と占有割合]
連続繊維強化樹脂成形体の厚さ方向断面(連続強化繊維の長さ方向に直交する断面)を任意の5か所について切り出し、エポキシ樹脂に包埋し、連続強化繊維が破損しないように注意しながら研磨を行った。
レーザーラマン顕微鏡(inViaQontor共焦点ラマンマイクロスコープ;株式会社レニショー)により該断面のマッピング画像を撮影し、得られた画像、スペクトルから、繊維強化樹脂に含まれる樹脂の種類を特定した。また、それぞれの面積をImageJによる画像処理によって算出し、連続強化繊維1本の端から、連続強化繊維1本の半径の10分の1の領域を占める樹脂の占有割合(面積比率)を算出した。また、該断面中の任意の10本の連続強化繊維について、連続強化繊維1本の半径の10分の1の領域を占める各樹脂の面積比率を算出し、その平均値を求めた。[Type and occupancy ratio of each thermoplastic resin in two or more types of fiber reinforced resin]
Cut out the thickness direction cross section of the continuous fiber reinforced resin molded body (cross section orthogonal to the length direction of the continuous reinforced fiber) at any five places and embed it in epoxy resin, taking care not to damage the continuous reinforced fiber. While polishing.
A mapping image of the cross section was taken with a laser Raman microscope (inViaQontor confocal Raman microscope; Renishaw Co., Ltd.), and the type of resin contained in the fiber-reinforced resin was identified from the obtained images and spectra. In addition, each area was calculated by image processing by ImageJ, and the occupancy ratio (area ratio) of the resin occupying one tenth of the radius of one continuous reinforcing fiber was calculated from the end of one continuous reinforcing fiber. .. Further, for any 10 continuous reinforcing fibers in the cross section, the area ratio of each resin occupying a region of 1/10 of the radius of one continuous reinforcing fiber was calculated, and the average value was calculated.
[繊維強化樹脂成形体における極界面領域以外の樹脂領域内での熱可塑性樹脂の分布]
連続繊維強化樹脂成形体を研磨機(小型精密試料作成システム IS-POLISHER ISPP-1000(株式会社池上精機))により、研磨面に125g/cm2の力がかかるように研磨した。研磨は耐水ペーパー番手#220で10分間、耐水ペーパー番手#1200で10分間、耐水ペーパー番手#2000で5分間、炭化ケイ素フィルム粒度9μmで10分間、アルミナフィルム粒度5μmで10分間、アルミナフィルム粒度3μmで5分間、アルミナフィルム粒度1μmで5分間、バフ研磨紙発泡ポリウレタンを用いた粒度0.1μmのコロイダルシリカ(バイカロックス0.1CR)で5分間の順番で行い、各研磨で約7mL/minで水を加えながら研磨した。研磨したサンプルを研磨面が潰れないように注意しながら、12タングスト(VI)リン酸n水和物5wt%水溶液に18時間浸漬して電子染色した。乾燥後、SEM(S-4700、株式会社日立ハイテクノロジーズ)により、任意の5か所の50μm×50μmの部分の熱可塑性樹脂の分布を観察し、それぞれの面積をimageJによる画像処理によって算出した。得られた分布により、極界面領域以外の樹脂領域内で特定樹脂が均一に分散しているか又は混合しているかを判定した。[Distribution of thermoplastic resin in the resin region other than the polar interface region in the fiber-reinforced resin molded product]
The continuous fiber reinforced resin molded product was polished by a polishing machine (small precision sample preparation system IS-POLISHER ISPP-1000 (Ikegami Seiki Co., Ltd.)) so that a force of 125 g / cm 2 was applied to the polished surface. Polishing is performed with water-resistant paper count # 220 for 10 minutes, water-resistant paper count # 1200 for 10 minutes, water-resistant paper count # 2000 for 5 minutes, silicon carbide film particle size 9 μm for 10 minutes, alumina film particle size 5 μm for 10 minutes, and alumina
[連続繊維強化樹脂成形体の損失正接の測定方法]
厚さ2mmの連続繊維強化樹脂成形体をバンドソーにより、繊維方向に対して0°、90°方向に幅5mm、長さ60mmに切削し、動的粘弾性測定装置(AresG2、TA Instruments株式会社)を用いて、窒素雰囲気下、測定温度範囲30℃~250℃、昇温速度5.0℃/分、角周波数10rad/s、変形モードをひねりモードで測定した。各温度における損失正接をプロットしたグラフのピークトップの値とその時の温度から、損失正接の値とその時の温度を得た。損失正接の値は低温側のピークトップの値とした。
[Measuring method of loss tangent of continuous fiber reinforced resin molded product]
A continuous fiber reinforced resin molded body with a thickness of 2 mm is cut with a band saw to a width of 5 mm and a length of 60 mm in the fiber direction at 0 ° and 90 °, and is a dynamic viscoelasticity measuring device (AresG2, TA Instruments Co., Ltd.). In a nitrogen atmosphere , the measurement temperature range was 30 ° C. to 250 ° C., the heating rate was 5.0 ° C./min, the angular frequency was 10 rad / s, and the deformation mode was measured in the twist mode. From the peak top value of the graph plotting the loss tangent at each temperature and the temperature at that time, the value of the loss tangent and the temperature at that time were obtained. The value of the loss tangent was the value of the peak top on the low temperature side.
[面衝撃試験]
成形体から長さ60mm、幅60mm、肉厚2mmの試験片を切り出し、高速衝撃試験機(島津 HYDRO SHOT HITS-P10、株式会社島津製作所)にて、JIS K7211-2;2006にのっとり、ストライカー径20mmφ、受け径40mmφ、試験速度4.4m/sec、試験温度23℃、試験数n=5で試験を行った。変位に対する試験力のグラフを書き、最大の衝撃力に達するまでの積分値を算出し、5サンプルの平均値を衝撃吸収エネルギーとした。[Surface impact test]
A test piece with a length of 60 mm, a width of 60 mm, and a wall thickness of 2 mm is cut out from the molded body, and a high-speed impact tester (Shimadzu HYDRO SHOT HITS-P10, Shimadzu Corporation) is used to follow JIS K7211-2; 2006, and the striker diameter. The test was performed at 20 mmφ, receiving diameter 40 mmφ, test speed 4.4 m / sec, test temperature 23 ° C., and test number n = 5. A graph of the test force for displacement was drawn, the integrated value until the maximum impact force was reached, and the average value of 5 samples was used as the impact absorption energy.
[連続繊維強化樹脂成形体のひねりモードの貯蔵弾性率の測定方法]
厚さ2mmの連続繊維強化樹脂成形体をバンドソーにより、繊維方向に対して0°、90°方向又は45°方向(斜め方向)に幅5mm、長さ60mmに切削し、動的粘弾性測定装置(AresG2、TA Instruments株式会社)を用いて、窒素雰囲気下、測定温度範囲30℃~250℃、昇温速度5.0℃/分、角周波数10rad/s、変形モードをひねりモードで測定した。各温度における貯蔵弾性率をプロットしたグラフのピークトップの値とその時の温度から、貯蔵弾性率の値とその時の温度を得た。
[Measurement method of storage elastic modulus in twist mode of continuous fiber reinforced resin molded product]
A dynamic viscoelasticity measuring device that cuts a continuous fiber reinforced resin molded body with a thickness of 2 mm into a width of 5 mm and a length of 60 mm in the 0 °, 90 °, or 45 ° directions (diagonal direction) with respect to the fiber direction with a band saw. Using (AresG2, TA Instruments Co., Ltd.), a measurement temperature range of 30 ° C. to 250 ° C., a heating rate of 5.0 ° C./min, an angular frequency of 10 rad / s, and a deformation mode were measured in a twist mode under a nitrogen atmosphere. From the peak top value of the graph plotting the storage elastic modulus at each temperature and the temperature at that time, the value of the storage elastic modulus and the temperature at that time were obtained.
[面衝撃試験]
成形体から長さ60mm、幅60mm、肉厚2mmの試験片を切り出し、高速衝撃試験機(島津 HYDRO SHOT HITS-P10、株式会社島津製作所)にて、JIS K7211-2;2006にのっとり、ストライカー径20mmφ、受け径40mmφ、試験速度4.4m/sec、試験温度23℃、試験数n=5で試験を行った。変位に対する試験力のグラフを書き、最大の衝撃強度を5サンプルの平均値で求めた。
[連続繊維強化樹脂成形体の曲げ貯蔵弾性率の測定方法]
厚さ2mmの連続繊維強化樹脂成形体をバンドソーにより、繊維方向に対して0°、90°方向又は45°方向(斜め方向)に幅5mm、長さ60mmに切削し、動的粘弾性測定装置(イプレクサー―500N、GABO社)を用いて、窒素雰囲気下、測定温度範囲25℃~250℃、昇温速度3.0℃/分、振動周波数8Hz、変形モードを曲げモードで測定し、最高値を曲げ貯蔵弾性率として得た。また、各温度における貯蔵弾性率を得た。
[Surface impact test]
A test piece with a length of 60 mm, a width of 60 mm, and a wall thickness of 2 mm is cut out from the molded body, and a high-speed impact tester (Shimadzu HYDRO SHOT HITS-P10, Shimadzu Corporation) is used to follow JIS K7211-2; 2006, and the striker diameter. The test was performed at 20 mmφ, receiving diameter 40 mmφ, test speed 4.4 m / sec, test temperature 23 ° C., and test number n = 5. A graph of the test force against displacement was drawn, and the maximum impact strength was obtained by averaging 5 samples.
[Measurement method of flexural modulus of continuous fiber reinforced resin molded product]
A dynamic elastic modulus measuring device is obtained by cutting a continuous fiber reinforced resin molded body having a thickness of 2 mm with a band saw into a width of 5 mm and a length of 60 mm in the 0 °, 90 ° or 45 ° directions (diagonal direction) with respect to the fiber direction. Using ( Iplexer -500N, GABO), the measurement temperature range is 25 ° C to 250 ° C, the temperature rise rate is 3.0 ° C / min, the vibration frequency is 8 Hz, and the deformation mode is measured in the bending mode. Was obtained as the bending storage elastic modulus. In addition, the storage elastic modulus at each temperature was obtained.
[連続繊維強化樹脂成形体の引張貯蔵弾性率、損失正接の測定方法]
厚さ2mmの連続繊維強化樹脂成形体をバンドソーにより、繊維方向に対して0°、90°方向に幅5mm、長さ60mmに切削し、動的粘弾性測定装置(イプレクサー―500N、GABO社)を用いて、窒素雰囲気下、測定温度範囲20℃~250℃、昇温速度3.0℃/分、振動周波数8Hz、変形モードを引張モードで測定し、各温度における貯蔵弾性率を得た。また、各温度における損失正接をプロットした際の20℃~200℃の間における極大値を引張損失正接とした。
[Measurement method of tensile storage elastic modulus and loss tangent of continuous fiber reinforced resin molded product]
A continuous fiber reinforced resin molded body with a thickness of 2 mm is cut with a band saw to a width of 5 mm and a length of 60 mm in the fiber direction at 0 ° and 90 °, and is a dynamic elastic modulus measuring device (Iplexer-500N, GABO). In a nitrogen atmosphere , the measurement temperature range was 20 ° C. to 250 ° C., the heating rate was 3.0 ° C./min, the vibration frequency was 8 Hz, and the deformation mode was measured in the tensile mode to obtain the storage elastic modulus at each temperature. Further, the maximum value between 20 ° C. and 200 ° C. when plotting the loss tangent at each temperature was defined as the tensile loss tangent.
[熱可塑性樹脂の融点と降温結晶化温度の測定方法]
2種以上の熱可塑性樹脂の混合物又は各々を、島津製作所製DSC-60を用い、試料量は約5mgとし、雰囲気ガスとしては30mL/分で流し、昇温温度は10℃/分の条件で室温(25℃)から予想される融点以上の温度まで加熱し溶融させ次いで、溶融したポリアミド樹脂を10℃/分で冷却させた際に観測される発熱ピークのピークトップの温度を結晶化温度とした。その後、10℃/分の速度で融点以上の温度まで再昇温した際に観測される吸熱ピークのピークトップの温度を融点とした。[Measurement method of melting point and crystallization temperature of thermoplastic resin]
A mixture of two or more types of thermoplastic resin or each of them is used under the conditions of DSC-60 manufactured by Shimadzu Corporation, the sample amount is about 5 mg, the atmosphere gas is 30 mL / min, and the temperature rise temperature is 10 ° C./min. The crystallization temperature is the temperature at the top of the exothermic peak observed when the molten polyamide resin is cooled at 10 ° C / min by heating it from room temperature (25 ° C) to a temperature above the expected melting point and melting it. bottom. After that, the temperature at the top of the endothermic peak observed when the temperature was re-heated to a temperature higher than the melting point at a rate of 10 ° C./min was taken as the melting point.
[強化繊維と各熱可塑性樹脂との結合力の測定]
連続繊維強化樹脂成形体を、強化繊維の長さ方向に直交する断面として30μmの厚さに切削し、連続強化繊維が破損しないように注意しながら研磨を行った。研磨したサンプルをナノインデンター(iMicro、Nanomechenics,Inc.)を用いて強化繊維を押し出すことにより、強化繊維と熱可塑性樹脂との結合力を測定した。熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)と強化繊維との間の結合力よりも、該樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)以外の樹脂(副樹脂)と強化繊維との間の結合力の方が大きい場合、「○」、弱い場合、「×」と判定した。[Measurement of bonding force between reinforcing fibers and each thermoplastic resin]
The continuous fiber reinforced resin molded body was cut to a thickness of 30 μm as a cross section orthogonal to the length direction of the reinforced fiber, and polished while being careful not to damage the continuous reinforced fiber. The bonded force between the reinforcing fiber and the thermoplastic resin was measured by extruding the reinforcing fiber from the polished sample using a nanoindenter (iMicro, Nanomechenics, Inc.). Of the thermoplastic resins, other than the resin (main resin) that occupies the highest overall resin region, rather than the binding force between the resin (main resin) that occupies the highest overall resin region and the reinforcing fiber. When the binding force between the resin (secondary resin) and the reinforcing fiber was larger, it was judged as “◯”, and when it was weak, it was judged as “×”.
[濡れ性、表面張力の測定]
280℃に加熱したホットプレート上で溶融した熱可塑性樹脂に連続強化繊維1本を埋め込み、マイクロスコープで観察しながら、1mm/秒で1mm連続強化繊維を引き抜いた際に、熱可塑性樹脂が連続繊維に引っ張られる長さによって評価した。熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)が強化繊維に引っ張られた長さよりも、該熱可塑性樹脂の内、該樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)以外の樹脂(副樹脂)が強化繊維に引っ張られた長さの方が大きい場合、濡れ性、表面張力を「○」、弱い場合、「×」と判定した。[Measurement of wettability and surface tension]
When one continuous reinforcing fiber is embedded in the melted thermoplastic resin on a hot plate heated to 280 ° C. and the 1 mm continuous reinforcing fiber is pulled out at 1 mm / sec while observing with a microscope, the thermoplastic resin becomes the continuous fiber. Evaluated by the length pulled by. Among the thermoplastic resins, the resin (main resin) having the highest occupancy ratio as a whole of the resin region has the highest occupancy ratio as a whole of the resin region among the thermoplastic resins than the length pulled by the reinforcing fiber. When the length of the resin (secondary resin) other than the resin (main resin) pulled by the reinforcing fiber was larger, the wettability and surface tension were judged to be “◯”, and when the resin (secondary resin) was weak, it was judged to be “x”.
[樹脂の溶融粘度の測定]
ツインキャピラリーレオメーター(ROSAND PRECISION)を用いて280℃においてシェアレトを100/s、200/s、400/s、1000/s、2000/s、4000/s、8000/sに変化させて測定を行った。シェアレト4000/sにおいて、2種以上の熱可塑性樹脂の混合物の溶融粘度が、前記2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂の粘度の4/5倍~5/4倍の場合に「○」、それ以外の場合に「×」と判定した。[Measurement of melt viscosity of resin]
Measurement was performed by changing the share to 100 / s, 200 / s, 400 / s, 1000 / s, 2000 / s, 4000 / s, and 8000 / s at 280 ° C. using a twin capillary rheometer (ROSAND PRESSION). rice field. At Sharelet 4000 / s, the melt viscosity of the mixture of two or more types of thermoplastic resin is 4/5 times or more the viscosity of the resin that occupies the highest proportion of the entire resin region among the above two types of thermoplastic resins. In the case of 5/4 times, it was judged as "○", and in other cases, it was judged as "×".
[熱可塑性樹脂の吸水率の測定]
カールフィッシャー水分計(京都電子工業株式会社、MKC610)を用いて窒素環境下、0.3g熱可塑性樹脂を量り取り、測定した。[Measurement of water absorption rate of thermoplastic resin]
A 0.3 g thermoplastic resin was weighed and measured in a nitrogen environment using a Karl Fischer Moisture Meter (Kyoto Electronics Manufacturing Co., Ltd., MKC610).
[熱可塑性樹脂の加熱プレス中の流動率の測定]
成形中に漏れ出した樹脂の重量を測り、元の熱可塑性樹脂の重量で割ることで求めた。
[連続繊維強化樹脂複合材料強化繊維の体積比率の測定]
連続繊維強化樹脂複合材料2gを切り出し、電気炉に入れ、温度650℃で3時間加熱して、樹脂を焼き飛ばした。その後、室温まで自然冷却し、残されたガラス繊維の質量を測定することで、連続繊維強化樹脂複合材料に含まれるガラス繊維と樹脂の比率を求めた。また、求めた比率から、密度で割りかえすことにより、連続繊維強化樹脂複合材料に対する強化繊維の体積比率(Vf)を求めた。[Measurement of flow rate of thermoplastic resin during heating press]
The weight of the resin leaked during molding was measured and divided by the weight of the original thermoplastic resin.
[Measurement of volume ratio of continuous fiber reinforced resin composite material reinforced fiber]
2 g of the continuous fiber reinforced resin composite material was cut out, placed in an electric furnace, and heated at a temperature of 650 ° C. for 3 hours to burn off the resin. Then, the glass fiber was naturally cooled to room temperature, and the mass of the remaining glass fiber was measured to determine the ratio of the glass fiber to the resin contained in the continuous fiber reinforced resin composite material. Further, the volume ratio (Vf) of the reinforced fiber to the continuous fiber reinforced resin composite material was obtained by dividing the obtained ratio by the density.
[熱可塑性樹脂中に拡散した集束剤の割合の測定]
連続繊維強化樹脂複合材料1gと連続強化繊維1gを、それぞれヘキサフルオロイソプロパノール(HFIP)20mLに浸漬し、撹拌ローラーで5時間撹拌して熱可塑性樹脂を溶解させた。溶け残ったものをHFIPで2度洗浄し、さらにHFIPに浸漬して、撹拌ローラーで5時間撹拌した。溶け残りをHFIPで2度洗浄し、真空乾燥したのち、XPS(Versa probeII、アルバックファイ株式会社)を用いて、励起源mono.AlKα 20kV×5mA 100W、分析サイズ100μm×1.4mm、光電子取出角で測定を行った。[Measurement of the proportion of sizing agent diffused in the thermoplastic resin]
1 g of the continuous fiber reinforced resin composite material and 1 g of the continuous reinforced fiber were immersed in 20 mL of hexafluoroisopropanol (HFIP), respectively, and stirred with a stirring roller for 5 hours to dissolve the thermoplastic resin. The undissolved material was washed twice with HFIP, further immersed in HFIP, and stirred with a stirring roller for 5 hours. The undissolved residue was washed twice with HFIP, vacuum dried, and then used with XPS (Versa probe II, ULVACPHI CO., LTD.) To excite source mono. Measurements were performed with AlKα 20 kV × 5 mA 100 W, analysis size 100 μm × 1.4 mm, and photoelectron extraction angle.
[末端官能基量の測定]
試料15mgをD2SO41.5mgに溶解させて、室温で1H-NMR(JEOL-ECZ500)測定を行い求めた。[Measurement of terminal functional group amount]
A 15 mg sample was dissolved in 1.5 mg of D 2 SO 4 and measured by 1 H-NMR (JEOL-ECZ500) at room temperature.
[アコースティックエミッション(AE)法測定]
アコースティックエミッション法測定は、長さ14mm(厚みの7倍)、幅10mmに切削した厚み2.0mmの連続繊維強化樹脂複合材料を、スパン間10mm(厚みの5倍)、試験速度1mm/minに設定した、層間せん断試験(JIS K7078)において、AEセンサー(AE-900M)を取り付けることにより、実施した。プリアンプを34dB、閾値を30dB、フィルタを95kHz-960kHzに設定し、AE振幅が50dB未満かつ、AE信号の持続時間が1000μs未満のAE信号を樹脂損傷相当、AE振幅が60dB以上かつ、AE信号の持続時間が1000μs以上のAE信号を層間剥離相当、AE振幅が50dB以上かつ、AE信号の持続時間が1000μs未満のAE信号をガラス繊維損傷相当として解析した。[Measurement by acoustic emission (AE) method]
For the acoustic emission method measurement, a continuous fiber reinforced resin composite material with a length of 14 mm (7 times the thickness) and a width of 10 mm and a thickness of 2.0 mm was used with a span spacing of 10 mm (5 times the thickness) and a test speed of 1 mm / min. In the set interlayer shear test (JIS K7078), it was carried out by attaching an AE sensor (AE-900M). The preamplifier is set to 34 dB, the threshold is set to 30 dB, the filter is set to 95 kHz to 960 kHz, the AE signal having an AE amplitude of less than 50 dB and the duration of the AE signal is less than 1000 μs is equivalent to resin damage, the AE amplitude is 60 dB or more, and the AE signal has an AE signal. An AE signal having a duration of 1000 μs or more was analyzed as equivalent to delamination, and an AE signal having an AE amplitude of 50 dB or more and a duration of AE signal of less than 1000 μs was analyzed as equivalent to glass fiber damage.
[μドロップ生成係数の測定]
μドロップ生成係数は、複合材界面特性評価装置(HM410、東栄産業株式会社)を用いて行い、装置の加熱炉部分に樹脂をセットし、炉内温度を樹脂の融点-40℃に設定し、装置にセットした、強化繊維の単糸1本に樹脂付けした。樹脂が未溶融で強化繊維に付着しなかった場合、樹脂が溶融するまで10℃ずつ炉内温度を上昇させ、強化繊維に樹脂付けを行った。強化繊維に溶融した樹脂を4回タッチさせ、樹脂を付着させたのち、1分間静置し、生成したμドロップの数を数え、下記式:
(μドロップ生成係数)={(生成したμドロップ数)/4}×10
により算出した。[Measurement of μ drop generation coefficient]
The μ drop generation coefficient was determined using a composite material interface characteristic evaluation device (HM410, Toei Sangyo Co., Ltd.), the resin was set in the heating furnace part of the device, and the temperature inside the furnace was set to the melting point of the resin -40 ° C. Resin was attached to one single yarn of the reinforcing fiber set in the apparatus. When the resin was unmelted and did not adhere to the reinforcing fibers, the temperature in the furnace was raised by 10 ° C. until the resin melted, and the reinforcing fibers were attached with the resin. After touching the molten resin to the reinforcing fiber four times to attach the resin, let it stand for 1 minute, count the number of μ drops generated, and use the following formula:
(Μ drop generation coefficient) = {(number of generated μ drops) / 4} × 10
Calculated by
[振動疲労試験]
ASTM-D1822引張衝撃ダンベルTypeSの試験片を用意し、EHF-EB50kN-40L(RV)(株式会社島津製作所)により、試験温度23℃、周波数20Hz、波形を正弦波、チャック間35mm、負荷最低荷重を負荷荷重の10%と設定して行った。[Vibration fatigue test]
Prepare a test piece of ASTM-D1822 tensile impact dumbbell TypeS, and use EHF-EB50kN-40L (RV) (Shimadzu Corporation) for test temperature 23 ° C, frequency 20Hz, waveform sine wave, chuck spacing 35mm, minimum load. Was set to 10% of the load.
[連続強化繊維]
[ガラス繊維(A)]
集束剤を0.45質量%付着させた、繊度11500dtexで単糸数2000本のガラス繊維を製造した。巻き取り形態はDWRであり、平均単糸径は17μmとした。
ガラス繊維集束剤は、γ-アミノプロピルトリエトキシシラン(以下、アミノシラン)KBE-903(信越化学工業株式会社製)0.5質量%、カルナウバワックスを1質量%、ポリウレタン樹脂Y65-55(株式会社ADEKA製)2質量%、無水マレイン酸40質量%、アクリル酸メチル50質量%、及びメタクリル酸メチル10質量%を共重合させ、重量平均分子量が20000である共重合化合物が3質量%、共重合化合物水溶液が3質量%となるように脱イオン水で調製することで作製した。
[ガラス繊維B]
繊度2900dtex、単糸数800本、平均単糸径13μmとした以外はガラス繊維(A)と同様のガラスを製造した。
[ガラス繊維C]
ER1200T-423(日本電気硝子株式会社)[Continuous reinforcement fiber]
[Glass fiber (A)]
A glass fiber having a fineness of 11500 dtex and a single yarn number of 2000 was produced with 0.45% by mass of a sizing agent attached. The winding form was DWR, and the average single yarn diameter was 17 μm.
The glass fiber sizing agent is γ-aminopropyltriethoxysilane (hereinafter, aminosilane) KBE-903 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 0.5% by mass, carnauba wax 1% by mass, polyurethane resin Y65-55 (stock). (Manufactured by ADEKA) 2% by mass, 40% by mass of maleic anhydride, 50% by mass of methyl acrylate, and 10% by mass of methyl methacrylate are copolymerized, and 3% by mass of the copolymer compound having a weight average molecular weight of 20000 is co-polymerized. It was prepared by preparing with deionized water so that the aqueous solution of the polymerized compound was 3% by mass.
[Glass fiber B]
A glass similar to that of the glass fiber (A) was produced except that the fineness was 2900 dtex, the number of single yarns was 800, and the average single yarn diameter was 13 μm.
[Glass fiber C]
ER1200T-423 (Nippon Electric Glass Co., Ltd.)
[熱可塑性樹脂]
ポリアミド樹脂A:ポリアミド66(レオナ1300S(旭化成(株)))、融点265℃、融解ピーク温度と降温結晶化ピーク温度の差(Tm-Tc)=53℃、カルボキシル末端基数は70μmol/g、アミノ末端基は32μmol/gであった(実施例6-)。
ポリアミド樹脂B:ポリアミド6/12(グリロンC CF6S(エムスケミージャパン(株)))、融点130℃
ポリアミド樹脂C:ポリアミド66(レオナ1402S(旭化成(株)))
又は
ポリアミド6(実施例4-、5-)(グリロンBS2 natural(エムスケミージャパン(株)))、融点225℃
ポリアミド6I(実施例5-):レオナR16024(旭化成(株))ガラス転移温度:130℃
ポリアミド6T/6I(実施例5-):東洋紡(株)試作品
ポリエチレン(PE)(実施例5-):サンテックJ240(旭化成(株))融点:125℃[Thermoplastic resin]
Polyamide resin A: Polyamide 66 (Leona 1300S (Asahi Kasei Co., Ltd.)), melting point 265 ° C., difference between melting peak temperature and temperature-decreasing crystallization peak temperature (Tm-Tc) = 53 ° C., carboxyl-terminal number of 70 μmol / g, amino The terminal group was 32 μmol / g (Example 6-).
Polyamide resin B: Polyamide 6/12 (Grillon C CF6S (Ms-Chemie Japan Co., Ltd.)), melting point 130 ° C.
Polyamide resin C: Polyamide 66 (Leona 1402S (Asahi Kasei Corporation))
Or
Polyamide 6 (Examples 4- and 5-) (Grillon BS2 natural (Mschemy Japan Co., Ltd.)), melting point 225 ° C.
Polyamide 6I (Example 5-): Leona R16024 (Asahi Kasei Corporation) Glass transition temperature: 130 ° C.
Polyamide 6T / 6I (Example 5-): Toyobo Co., Ltd. Prototype Polyethylene (PE) (Example 5-): Suntech J240 (Asahi Kasei Co., Ltd.) Melting point: 125 ° C.
[ポリアミドフィルム]
前記熱可塑性樹脂A及び/又はBを、Tダイ押し出し成形機(株式会社創研製)を用いて成形することでフィルムを得た。フィルムの厚さは100μmであった。[Polyamide film]
A film was obtained by molding the thermoplastic resins A and / or B using a T-die extrusion molding machine (manufactured by Soken Co., Ltd.). The thickness of the film was 100 μm.
[ガラスクロス、炭素繊維布帛]
レピア織機(織幅2m)を用い、前記ガラス繊維を経糸、緯糸として用いて製織することでガラスクロスを製造した。得られたガラスクロスの織形態は、平織、織密度は6.5本/25mm、目付は600g/m2であった。
ガラスクロス(実施例5-):WFR 350 100BS6(日東紡(株))
炭素繊維布帛(実施例5-):ポリビニルピロリドンを2.8質量%付着させた、繊度8000dtexで単糸数12000本の炭素繊維を製造し、その後レピア織機を用いて製織(平織)した。[Glass cloth, carbon fiber cloth]
A glass cloth was manufactured by weaving using the glass fiber as a warp and a weft using a rapier loom (weaving width 2 m). The woven form of the obtained glass cloth was plain weave, the weaving density was 6.5 lines / 25 mm, and the basis weight was 600 g / m 2 .
Glass cloth (Example 5-): WFR 350 100BS6 (Nitto Boseki Co., Ltd.)
Carbon fiber fabric (Example 5-): Carbon fibers having 12,000 single yarns were produced at a fineness of 8000 dtex to which 2.8% by mass of polyvinylpyrrolidone was attached, and then weaved (plain weave) using a rapier loom.
[粒子状添加材]
粒子状添加材としてカーボンブラックを含むマスターバッチ(旭化成(株))を用いた。カーボンブラックは3wt%含まれていた。[Particulate matter]
A masterbatch containing carbon black (Asahi Kasei Corporation) was used as a particulate additive. Carbon black was contained in 3 wt%.
[連続繊維強化樹脂成形体の製造]
成形機として、最大型締め力50トンの油圧成形機(株式会社ショージ)を使用した。平板型の連続繊維強化樹脂成形体(縦200mm、横100mm、肉厚2mm)を得るためのインロー構造の金型を準備した。
前記ガラスクロスと前記ポリアミドフィルムを金型形状に合わせて切断し、所定枚数重ね、金型内に設置した。
成形機内温度を330℃に加熱し、次いで型締め力5MPaで型締めし、圧縮成形を行った。成形時間はポリアミド66の融点である265℃に達してから1分とし、金型を急冷したのちに金型を開放し、成形体を取り出した。成形中の最大温度は275℃であった。[Manufacturing of continuous fiber reinforced resin molded product]
As a molding machine, a hydraulic molding machine (Shoji Co., Ltd.) with a maximum mold clamping force of 50 tons was used. A mold having an inlay structure for obtaining a flat plate type continuous fiber reinforced resin molded body (length 200 mm, width 100 mm,
The glass cloth and the polyamide film were cut according to the shape of the mold, stacked in a predetermined number, and installed in the mold.
The temperature inside the molding machine was heated to 330 ° C., then the mold was compacted with a mold clamping force of 5 MPa, and compression molding was performed. The molding time was set to 1 minute after reaching the melting point of 265 ° C. of the polyamide 66, the mold was rapidly cooled, the mold was opened, and the molded product was taken out. The maximum temperature during molding was 275 ° C.
[ダブルベルトプレス装置による製造]
成形機として、ダブルベルトプレス装置(プロセスシステム株式会社)を使用した。前記ガラスクロス5枚と前記ポリアミドフィルム10本をロールから繰り出した。装置加熱部温度を330℃とし、冷却は水冷で行った。圧力30kNで加圧し、0.2m/minで搬送した。[Manufactured by double belt press device]
A double belt press device (Process System Co., Ltd.) was used as the molding machine. Five glass cloths and ten polyamide films were unwound from the roll. The temperature of the heating part of the device was 330 ° C., and the cooling was performed by water cooling. It was pressurized at a pressure of 30 kN and conveyed at 0.2 m / min.
[実施例1-1]
ガラスクロス6枚とポリアミド樹脂Aのフィルム7枚を重ねて成形を行った。成形時間はポリアミド66の融点である265℃に達してから1分とし、金型を急冷した後に金型を開放し、成形体を取り出した。成形中の最大温度は285℃であった。[Example 1-1]
Six glass cloths and seven films of polyamide resin A were laminated and molded. The molding time was set to 1 minute after reaching the melting point of 265 ° C. of the polyamide 66, the mold was rapidly cooled, the mold was opened, and the molded product was taken out. The maximum temperature during molding was 285 ° C.
[実施例1-2]
ガラスクロス6枚とポリアミド樹脂Aのフィルム7枚を重ねて成形を行った。成形機内の温度を300℃に設定し、成形時間はポリアミド66の融点である265℃に達してから15分とし、金型を急冷した後に金型を開放し、成形体を取り出した。成形中の最大温度は300℃であった。[Example 1-2]
Six glass cloths and seven films of polyamide resin A were laminated and molded. The temperature inside the molding machine was set to 300 ° C., the molding time was 15 minutes after reaching the melting point of the polyamide 66 of 265 ° C., the mold was rapidly cooled, the mold was opened, and the molded product was taken out. The maximum temperature during molding was 300 ° C.
[実施例1-3]
265℃に達してから30秒の成形としたこと以外は実施例1-1と同様にして連続繊維強化樹脂成形体を得た。成形中の最大温度は280℃であった。[Example 1-3]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 1-1 except that the molding was carried out for 30 seconds after reaching 265 ° C. The maximum temperature during molding was 280 ° C.
[実施例1-4]
ポリアミドフィルムが、ポリアミド樹脂Aとポリアミド樹脂Bのドライブレンド品(A:B=8:1)からできていること以外は、実施例1-1と同様にして連続繊維強化樹脂成形体を得た。[Example 1-4]
A continuous fiber reinforced resin molded body was obtained in the same manner as in Example 1-1 except that the polyamide film was made of a dry blend product of polyamide resin A and polyamide resin B (A: B = 8: 1). ..
[実施例1-5]
ポリアミド樹脂Aのフィルムに代えて、エポキシ樹脂を用いたこと以外は、実施例1-2と同様にして連続繊維強化樹脂成形体を得た。
集束剤として3-グリシドキシプロピルトリメトキシシラン(KBM-402、信越化学工業株式会社)0.3質量%、エポキシ樹脂エマルジョン1.5質量%、カルナウバワックスを0.2質量%付着させた前記ガラス繊維を用いてガラスクロスを製造した。このガラスクロスを6枚積層させて金型に設置し、そこにビスフェノールA型液状エポキシ樹脂(jER828、三菱化学(株))16gとビスフェノールA(4、4′-(プロパンー2,2-ジイル)ジフェノール1.6gを投入し、成形機内の温度を40℃に設定し、型締め力5MPaで3日間圧縮成形を行い、連続繊維強化樹脂成形体を得た。[Example 1-5]
A continuous fiber reinforced resin molded body was obtained in the same manner as in Example 1-2 except that an epoxy resin was used instead of the film of the polyamide resin A.
As a sizing agent, 3-glycidoxypropyltrimethoxysilane (KBM-402, Shin-Etsu Chemical Co., Ltd.) 0.3% by mass, epoxy resin emulsion 1.5% by mass, and carnauba wax 0.2% by mass were adhered. A glass cloth was produced using the glass fiber. Six pieces of this glass cloth are laminated and installed in a mold, and bisphenol A type liquid epoxy resin (jER828, Mitsubishi Chemical Co., Ltd.) 16 g and bisphenol A (4,4'-(propane-2,2-diyl)) are placed therein. 1.6 g of diphenol was added, the temperature inside the molding machine was set to 40 ° C., and compression molding was performed for 3 days with a mold clamping force of 5 MPa to obtain a continuous fiber reinforced resin molded body.
[実施例1-6]
ガラスクロスの枚数を5枚、ポリアミド樹脂Aのフィルムの枚数を10枚にしたこと以外は、実施例1-1と同様にして連続繊維強化樹脂成形体を得た。[Example 1-6]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 1-1 except that the number of glass cloths was 5 and the number of films of the polyamide resin A was 10.
[比較例1-1]
集束剤を添加していないガラス繊維を用いたこと以外は、実施例1-1と同様にして連続繊維強化樹脂成形体を得た。[Comparative Example 1-1]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 1-1 except that the glass fiber to which the sizing agent was not added was used.
[比較例1-2]
集束剤としてシランカップリング剤として3-グリシドキシプロピルトリメトキシシラン0.3質量%、エポキシ樹脂エマルジョン1.5質量%、カルナウバワックス0.2質量%を付着させたガラス繊維を用いたこと以外は、実施例1-1と同様にして連続繊維強化樹脂成形体を得た。[Comparative Example 1-2]
As a sizing agent, a glass fiber to which 3-glycidoxypropyltrimethoxysilane 0.3% by mass, an epoxy resin emulsion 1.5% by mass, and carnauba wax 0.2% by mass was attached was used as a silane coupling agent. A continuous fiber reinforced resin molded body was obtained in the same manner as in Example 1-1 except for the above.
[比較例1-3]
ポリアミド66をガラスクロスに含浸したBond Laminate製「Tepex dynalite 101」に関して、実施例1-1と同様の評価を行った。[Comparative Example 1-3]
The same evaluation as in Example 1-1 was performed on "Tepex dynarite 101" manufactured by Bond Laminate in which polyamide 66 was impregnated into a glass cloth.
[比較例1-6]
成形機内温度を265℃に設定し、成形したこと以外は、実施例1-2と同様にして連続繊維強化樹脂成形体を得た。成形中の最大温度は265℃であった。[Comparative Example 1-6]
A continuous fiber reinforced resin molded body was obtained in the same manner as in Example 1-2 except that the temperature inside the molding machine was set to 265 ° C. and molding was performed. The maximum temperature during molding was 265 ° C.
上記表1から、実施例1-1~6の連続繊維強化樹脂成形体は、連続強化繊維1本の端から、連続強化繊維1本の半径の10分の1の領域の空隙率が10%以下であるものが全体の10%以上である連続繊維強化樹脂であるため、非常に高い引張応力、曲げ応力、曲げ弾性率を示した。これらの物性は、比較例1-3における市販品の中間材料を用いて得た成形体の物性よりも、かなり良いものであった。
比較例1-1、2のように、集束剤を塗布していない連続強化繊維又は樹脂との相性が悪い集束剤を塗布した連続強化繊維を用いた場合には、空隙率が10%より大きくなり、引張応力、曲げ応力、曲げ弾性率が低下した。
比較例1-6のように、成形温度が低いと、空隙率が10%より大きくなり、引張応力、曲げ応力、曲げ弾性率が低下した。From Table 1 above, the continuous fiber reinforced resin molded bodies of Examples 1-1 to 6 have a void ratio of 10% in the region of 1/10 of the radius of one continuous reinforcing fiber from the end of one continuous reinforcing fiber. Since the following are continuous fiber reinforced plastics which account for 10% or more of the total, they showed extremely high tensile stress, bending stress, and flexural modulus. These physical properties were considerably better than those of the molded product obtained by using the commercially available intermediate material in Comparative Example 1-3.
When a continuous reinforcing fiber not coated with a sizing agent or a continuously reinforced fiber coated with a sizing agent having a bad compatibility with a resin is used as in Comparative Examples 1-1 and 2, the porosity is larger than 10%. As a result, tensile stress, bending stress, and flexural modulus decreased.
When the molding temperature was low as in Comparative Example 1-6, the porosity became larger than 10%, and the tensile stress, bending stress, and bending elastic modulus decreased.
[実施例2-1]
ガラスクロス6枚とポリアミド樹脂Aのフィルム7枚を重ねて成形を行った。成形時間はポリアミド66の融点である265℃に達してから1分とし、金型を急冷した後に金型を開放し、成形体を取り出した。成形中の最大温度は285℃であった。[Example 2-1]
Six glass cloths and seven films of polyamide resin A were laminated and molded. The molding time was set to 1 minute after reaching the melting point of 265 ° C. of the polyamide 66, the mold was rapidly cooled, the mold was opened, and the molded product was taken out. The maximum temperature during molding was 285 ° C.
[実施例2-2]
ガラスクロス6枚とポリアミド樹脂Aのフィルム7枚を重ねて成形を行った。成形機内の温度を300℃に設定し、成形時間はポリアミド66の融点である265℃に達してから10分とし、金型を急冷した後に金型を開放し、成形体を取り出した。成形中の最大温度は300℃であった。[Example 2-2]
Six glass cloths and seven films of polyamide resin A were laminated and molded. The temperature inside the molding machine was set to 300 ° C., the molding time was 10 minutes after reaching the melting point of the polyamide 66 of 265 ° C., the mold was rapidly cooled, the mold was opened, and the molded product was taken out. The maximum temperature during molding was 300 ° C.
[実施例2-3]
265℃に達してから30秒の成形としたこと以外は、実施例2-1と同様にして連続繊維強化樹脂成形体を得た。成形中の最大温度は280℃であった。[Example 2-3]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 2-1 except that the molding was carried out for 30 seconds after reaching 265 ° C. The maximum temperature during molding was 280 ° C.
[実施例2-4]
ポリアミドフィルムが、ポリアミド樹脂Bのフィルムであること以外は、実施例2-1と同様にして連続繊維強化樹脂成形体を得た。[Example 2-4]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 2-1 except that the polyamide film was a film of polyamide resin B.
[実施例2-5]
ガラスクロスの枚数を5枚、ポリアミド樹脂Aのフィルムの枚数を10枚にしたこと以外は、実施例2-1と同様にして連続繊維強化樹脂成形体を得た。[Example 2-5]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 2-1 except that the number of glass cloths was 5 and the number of films of the polyamide resin A was 10.
[実施例2-6]
ガラスクロスの枚数を5枚、ポリアミド樹脂Aのフィルムの枚数を10枚にしたこと以外は、実施例2-2と同様にして連続繊維強化樹脂成形体を得た。[Example 2-6]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 2-2, except that the number of glass cloths was 5 and the number of films of the polyamide resin A was 10.
[比較例2-1]
集束剤を添加していないガラス繊維を用いたこと以外は、実施例2-1と同様にして連続繊維強化樹脂成形体を得た。[Comparative Example 2-1]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 2-1 except that the glass fiber to which the sizing agent was not added was used.
[比較例2-2]
集束剤としてシランカップリング剤として3-グリシドキシプロピルトリメトキシシラン0.3質量%、エポキシ樹脂エマルジョン1.5質量%、カルナウバワックス0.2質量%を付着させたガラス繊維を用いたこと以外は、実施例2-6と同様にして連続繊維強化樹脂成形体を得た。[Comparative Example 2-2]
As a sizing agent, a glass fiber to which 3-glycidoxypropyltrimethoxysilane 0.3% by mass, an epoxy resin emulsion 1.5% by mass, and carnauba wax 0.2% by mass was attached was used as a silane coupling agent. A continuous fiber reinforced resin molded body was obtained in the same manner as in Example 2-6 except for the above.
[比較例2-3]
ポリアミド66をガラスクロスに含浸したBond Laminate製「Tepex dynalite 101」に関して、実施例2-1と同様の評価を行った。[Comparative Example 2-3]
The same evaluation as in Example 2-1 was performed on "Tepex dynarite 101" manufactured by Bond Laminate in which polyamide 66 was impregnated into a glass cloth.
上記表2から、実施例2-1~6の連続繊維強化樹脂成形体は、ひねりモードの損失正接が0.11以下であるため、非常に高い衝撃吸収エネルギーを示した。これらの物性は、比較例2-3における市販品の中間材料を用いて得た成形体の物性よりも、かなり良いものであった。
比較例のように、損失正接が高いと、衝撃吸収エネルギーが低下した。From Table 2 above, the continuous fiber reinforced resin molded bodies of Examples 2-1 to 6 showed extremely high impact absorption energy because the loss tangent in the twist mode was 0.11 or less. These physical properties were considerably better than those of the molded product obtained by using the commercially available intermediate material in Comparative Example 2-3.
As in the comparative example, when the loss tangent was high, the impact absorption energy decreased.
[実施例3-1]
ガラスクロス6枚とポリアミド樹脂Aのフィルム7枚を重ねて成形を行った。成形時間はポリアミド66の融点である265℃に達してから1分とし、金型を急冷した後に金型を開放し、成形体を取り出した。成形中の最大温度は285℃であった。[Example 3-1]
Six glass cloths and seven films of polyamide resin A were laminated and molded. The molding time was set to 1 minute after reaching the melting point of 265 ° C. of the polyamide 66, the mold was rapidly cooled, the mold was opened, and the molded product was taken out. The maximum temperature during molding was 285 ° C.
[実施例3-2]
ガラスクロス6枚とポリアミド樹脂Aのフィルム7枚を重ねて成形を行った。成形機内の温度を300℃に設定し、成形時間はポリアミド66の融点である265℃に達してから10分とし、金型を急冷した後に金型を開放し、成形体を取り出した。成形中の最大温度は300℃であった。[Example 3-2]
Six glass cloths and seven films of polyamide resin A were laminated and molded. The temperature inside the molding machine was set to 300 ° C., the molding time was 10 minutes after reaching the melting point of the polyamide 66 of 265 ° C., the mold was rapidly cooled, the mold was opened, and the molded product was taken out. The maximum temperature during molding was 300 ° C.
[実施例3-3]
265℃に達してから30秒の成形としたこと以外は実施例3-1と同様にして連続繊維強化樹脂成形体を得た。成形中の最大温度は280℃であった。[Example 3-3]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 3-1 except that the molding was carried out for 30 seconds after reaching 265 ° C. The maximum temperature during molding was 280 ° C.
[実施例3-4]
ポリアミドフィルムが、ポリアミド樹脂Bのフィルムであること以外は、実施例3-1と同様にして連続繊維強化樹脂成形体を得た。[Example 3-4]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 3-1 except that the polyamide film was a film of polyamide resin B.
[実施例3-5]
ガラスクロスの枚数を5枚、ポリアミド樹脂Aのフィルムの枚数を10枚にしたこと以外は、実施例3-1と同様にして連続繊維強化樹脂成形体を得た。[Example 3-5]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 3-1 except that the number of glass cloths was 5 and the number of films of the polyamide resin A was 10.
[実施例3-6]
ガラスクロスの枚数を5枚、ポリアミド樹脂Aのフィルムの枚数を10枚にしたこと以外は、実施例3-2と同様にして連続繊維強化樹脂成形体を得た。[Example 3-6]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 3-2, except that the number of glass cloths was 5 and the number of films of the polyamide resin A was 10.
[比較例3-1]
集束剤を添加していないガラス繊維を用いたこと以外は、実施例3-1と同様にして連続繊維強化樹脂成形体を得た。[Comparative Example 3-1]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 3-1 except that the glass fiber to which the sizing agent was not added was used.
[比較例3-2]
集束剤としてシランカップリング剤として3-グリシドキシプロピルトリメトキシシラン0.3質量%、エポキシ樹脂エマルジョン1.5質量%、カルナウバワックス0.2質量%を付着させたガラス繊維を用いたこと以外は、実施例3-6と同様にして連続繊維強化樹脂成形体を得た。[Comparative Example 3-2]
As a sizing agent, a glass fiber to which 3-glycidoxypropyltrimethoxysilane 0.3% by mass, an epoxy resin emulsion 1.5% by mass, and carnauba wax 0.2% by mass was attached was used as a silane coupling agent. A continuous fiber reinforced resin molded body was obtained in the same manner as in Example 3-6 except for the above.
[比較例3-3]
ポリアミド66をガラスクロスに含浸したBond Laminate製「Tepex dynalite 101」に関して、実施例3-1と同様の評価を行った。[Comparative Example 3-3]
The same evaluation as in Example 3-1 was performed on "Tepex dynarite 101" manufactured by Bond Laminate in which polyamide 66 was impregnated into a glass cloth.
上記表3から、実施例3-1~6の連続繊維強化樹脂成形体は、ひねりモードの貯蔵弾性率が3.4GPa以上であるため、非常に高い衝撃強度を示した。これらの物性は、比較例3-3における市販品の中間材料を用いて得た成形体の物性よりも、かなり良いものであった。
比較例のようにひねりモードの貯蔵弾性率が低いと、衝撃強度が低下した。From Table 3 above, the continuous fiber reinforced resin molded bodies of Examples 3-1 to 6 showed a very high impact strength because the storage elastic modulus in the twist mode was 3.4 GPa or more. These physical properties were considerably better than those of the molded product obtained by using the commercially available intermediate material in Comparative Example 3-3.
When the storage elastic modulus in the twist mode was low as in the comparative example, the impact strength decreased.
[実施例4-1]
ガラスクロス5枚とポリアミド樹脂Aのフィルム10枚を重ねて成形を行った。成形機内の温度を300℃に設定し、成形時間はポリアミド66の融点である265℃に達してから10分とし、金型を急冷した後に金型を開放し、成形体を取り出した。成形中の最大温度は300℃であった。このときの曲げ貯蔵弾性率は31GPa、150℃における曲げ貯蔵弾性率は24GPa(保持率77%)、斜めに切削した際の曲げ貯蔵弾性率は20GPa(保持率64%)、50℃における引張貯蔵弾性率は25GPa、引張損失正接は0.033、引張貯蔵弾性率と曲げ貯蔵弾性率が逆転する温度は115℃、{30℃における(引張貯蔵弾性率―曲げ貯蔵弾性率)}/{200℃における(曲げ貯蔵弾性率―引張貯蔵弾性率)}の値は2.3であり、衝撃強度は8.50kNであった。[Example 4-1]
Molding was performed by stacking 5 glass cloths and 10 films of polyamide resin A. The temperature inside the molding machine was set to 300 ° C., the molding time was 10 minutes after reaching the melting point of the polyamide 66 of 265 ° C., the mold was rapidly cooled, the mold was opened, and the molded product was taken out. The maximum temperature during molding was 300 ° C. The flexural modulus at this time is 31 GPa, the flexural modulus at 150 ° C. is 24 GPa (retention rate 77%), the flexural modulus when cutting diagonally is 20 GPa (retention rate 64%), and tensile storage at 50 ° C. Elastic modulus is 25 GPa, tensile loss tangent is 0.033, tensile storage elastic modulus and bending storage elastic modulus are reversed at 115 ° C, {at 30 ° C (tensile storage elastic modulus-bending storage elastic modulus)} / {200 ° C. The value of (bending storage elastic modulus-tensile storage elastic modulus)} was 2.3, and the impact strength was 8.50 kN.
[実施例4-2]
ガラスクロス6枚とポリアミド樹脂Aのフィルム7枚を重ねて成形を行った。成形機内の温度を300℃に設定し、成形時間はポリアミド66の融点である265℃に達してから10分とし、金型を急冷した後に金型を開放し、成形体を取り出した。成形中の最大温度は300℃であった。このときの曲げ貯蔵弾性率は37GPaであり、衝撃強度は9.25kNであった。[Example 4-2]
Six glass cloths and seven films of polyamide resin A were laminated and molded. The temperature inside the molding machine was set to 300 ° C., the molding time was 10 minutes after reaching the melting point of the polyamide 66 of 265 ° C., the mold was rapidly cooled, the mold was opened, and the molded product was taken out. The maximum temperature during molding was 300 ° C. The flexural modulus at this time was 37 GPa, and the impact strength was 9.25 kN.
[実施例4-3]
265℃に達してから30秒の成形としたこと以外は、実施例4-2と同様にして連続繊維強化樹脂成形体を得た。成形中の最大温度は280℃であった。このときの曲げ貯蔵弾性率は28GPaであり、衝撃強度は8.81kNであった。[Example 4-3]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 4-2 except that the molding was carried out for 30 seconds after reaching 265 ° C. The maximum temperature during molding was 280 ° C. The flexural modulus at this time was 28 GPa, and the impact strength was 8.81 kN.
[実施例4-4]
ポリアミドフィルムが、ポリアミド樹脂Bのフィルムであること以外は、実施例4-2と同様にして連続繊維強化樹脂成形体を得た。このときの曲げ貯蔵弾性率は33GPaであり、衝撃強度は9.05kNであった。[Example 4-4]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 4-2 except that the polyamide film was a film of polyamide resin B. The flexural modulus at this time was 33 GPa, and the impact strength was 9.05 kN.
[実施例4-5]
265℃に達してから1分の成形としたこと以外は、実施例4-1と同様にして連続繊維強化樹脂成形体を得た。成形中の最大温度は285℃であった。このときの曲げ貯蔵弾性率は31GPaであり、衝撃強度は8.50kNであった。[Example 4-5]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 4-1 except that the molding was carried out for 1 minute after reaching 265 ° C. The maximum temperature during molding was 285 ° C. The flexural modulus at this time was 31 GPa, and the impact strength was 8.50 kN.
[実施例4-6]
ガラスクロス6枚とポリアミド樹脂Aのフィルム7枚を重ねて成形を行った。成形時間はポリアミド66の融点である265℃に達してから1分とし、金型を急冷した後に金型を開放し、成形体を取り出した。成形中の最大温度は285℃であった。このときの曲げ貯蔵弾性率は36GPaであり、衝撃強度は9.10kNであった。[Example 4-6]
Six glass cloths and seven films of polyamide resin A were laminated and molded. The molding time was set to 1 minute after reaching the melting point of 265 ° C. of the polyamide 66, the mold was rapidly cooled, the mold was opened, and the molded product was taken out. The maximum temperature during molding was 285 ° C. The flexural modulus at this time was 36 GPa, and the impact strength was 9.10 kN.
[比較例4-1]
集束剤を添加していないガラス繊維を用いたこと以外は、実施例6と同様にして連続繊維強化樹脂成形体を得た。このときの曲げ貯蔵弾性率は15GPaであり、衝撃強度は3.20kNであった。[Comparative Example 4-1]
A continuous fiber reinforced resin molded product was obtained in the same manner as in Example 6 except that the glass fiber to which the sizing agent was not added was used. The flexural modulus at this time was 15 GPa, and the impact strength was 3.20 kN.
[比較例4-2]
集束剤としてシランカップリング剤として3-グリシドキシプロピルトリメトキシシラン0.3質量%、エポキシ樹脂エマルジョン1.5質量%、カルナウバワックス0.2質量%を付着させたガラス繊維を用いたこと以外は、実施例4-1と同様にして連続繊維強化樹脂成形体を得た。このときの曲げ貯蔵弾性率は20GPaであり、衝撃強度は5.21kNであった。[Comparative Example 4-2]
As a sizing agent, a glass fiber to which 3-glycidoxypropyltrimethoxysilane 0.3% by mass, an epoxy resin emulsion 1.5% by mass, and carnauba wax 0.2% by mass was attached was used as a silane coupling agent. A continuous fiber reinforced resin molded body was obtained in the same manner as in Example 4-1 except for the above. The flexural modulus at this time was 20 GPa, and the impact strength was 5.21 kN.
[比較例4-3]
ポリアミド66をガラスクロスに含浸したBond Laminate製「Tepex dynalite 101」に関して、実施例4-1と同様の評価を行った。このときの曲げ貯蔵弾性率は20.8GPa、150℃における曲げ貯蔵弾性率は15.7GPa(保持率75%)、斜めに切削した際の曲げ貯蔵弾性率は11.9GPa(保持率57%)、50℃における引張貯蔵弾性率は21GPa、引張損失正接は0.038、引張貯蔵弾性率と曲げ貯蔵弾性率が逆転する温度は90℃、{30℃における(引張貯蔵弾性率―曲げ貯蔵弾性率)}/{200℃における(曲げ貯蔵弾性率―引張貯蔵弾性率)}の値は0.57であり、衝撃強度は5.32kNであった。[Comparative Example 4-3]
The same evaluation as in Example 4-1 was performed on "Tepex dynarite 101" manufactured by Bond Laminate in which polyamide 66 was impregnated into a glass cloth. The flexural modulus at this time is 20.8 GPa, the flexural modulus at 150 ° C. is 15.7 GPa (retention rate 75%), and the flexural modulus when cutting diagonally is 11.9 GPa (retention rate 57%). , The tensile storage elastic modulus at 50 ° C is 21 GPa, the tensile loss tangent is 0.038, the temperature at which the tensile storage elastic modulus and the bending storage elastic modulus are reversed is 90 ° C. )} / {(Bending storage elastic modulus-tensile storage elastic modulus)} at 200 ° C. was 0.57, and the impact strength was 5.32 kN.
実施例4-1~6の連続繊維強化樹脂成形体は、曲げ貯蔵弾性率が22GPa以上であるため、非常に高い衝撃強度を示した。これらの物性は、比較例4-3における市販品の中間材料を用いて得た成形体の物性よりも、かなり良いものであった。
比較例のように曲げ貯蔵弾性率が低いと、衝撃強度が低下した。Since the continuous fiber reinforced resin molded bodies of Examples 4-1 to 6 had a flexural modulus of 22 GPa or more, they showed extremely high impact strength. These physical properties were considerably better than those of the molded product obtained by using the commercially available intermediate material in Comparative Example 4-3.
When the flexural modulus of storage was low as in the comparative example, the impact strength decreased.
[実施例5-1]
PA66とPA6/12を重量比8:1でドライブレンドしたものを用いて熱可塑性樹脂フィルムを製造した。このフィルムの厚さは100μmであった。このフィルム11枚とガラスクロス10枚を交互に積層し、成形を行った。ガラス繊維との極界面領域以外の樹脂領域内ではPA6/12がPA66に均一に分散していた。[Example 5-1]
A thermoplastic resin film was produced using a dry blend of PA66 and PA6 / 12 at a weight ratio of 8: 1. The thickness of this film was 100 μm. 11 sheets of this film and 10 sheets of glass cloth were alternately laminated and molded. PA6 / 12 was uniformly dispersed in PA66 in the resin region other than the polar interface region with the glass fiber.
[実施例5-2]
PA6/12の代わりにPA6を用いたこと以外は、実施例5-1と同様に連続繊維強化樹脂成形体を製造した。ガラス繊維との極界面領域以外の樹脂領域内ではPA6がPA66に均一に分散していた。[Example 5-2]
A continuous fiber reinforced resin molded product was produced in the same manner as in Example 5-1 except that PA6 was used instead of PA6 / 12. PA6 was uniformly dispersed in PA66 in the resin region other than the polar interface region with the glass fiber.
[実施例5-3]
PA6/12の代わりにPEを用いたこと以外は、実施例5-1と同様に連続繊維強化樹脂成形体を製造した。ガラス繊維との極界面領域以外の樹脂領域内ではPEがPA66に均一に分散していた。[Example 5-3]
A continuous fiber reinforced resin molded product was produced in the same manner as in Example 5-1 except that PE was used instead of PA6 / 12. PE was uniformly dispersed in PA66 in the resin region other than the polar interface region with the glass fiber.
[実施例5-4]
PA6/12の代わりにPA6Iを用いたこと以外は、実施例5-1と同様に連続繊維強化樹脂成形体を製造した。ガラス繊維との極界面領域以外の樹脂領域内でPA6IがPA66に均一に分散していた。[Example 5-4]
A continuous fiber reinforced resin molded product was produced in the same manner as in Example 5-1 except that PA6I was used instead of PA6 / 12. PA6I was uniformly dispersed in PA66 in the resin region other than the polar interface region with the glass fiber.
[実施例5-5]
PA66とPA6/12を重量比5:4でドライブレンドしたこと以外は、実施例5-1と同様に連続繊維強化樹脂成形体を製造した。ガラス繊維との極界面領域以外の樹脂領域内ではPA6/12がPA66に均一に分散していた。[Example 5-5]
A continuous fiber reinforced resin molded product was produced in the same manner as in Example 5-1 except that PA66 and PA6 / 12 were dry-blended at a weight ratio of 5: 4. PA6 / 12 was uniformly dispersed in PA66 in the resin region other than the polar interface region with the glass fiber.
[実施例5-6]
二軸押出機(TEM26SS、東芝機械)を用いて仕込み比(重量比)8:1でPA66とPA6/12を予め混練したものを用いて熱可塑性樹脂フィルムを製造したこと以外は、実施例5-1と同様に連続繊維強化樹脂成形体を製造した。ガラス繊維との極界面領域以外の樹脂領域内ではPA6/12がPA66に均一に分散していた。[Example 5-6]
Example 5 except that a thermoplastic resin film was produced by pre-kneading PA66 and PA6 / 12 at a charging ratio (weight ratio) of 8: 1 using a twin-screw extruder (TEM26SS, Toshiba Machine Co., Ltd.). A continuous fiber reinforced resin molded product was produced in the same manner as in -1. PA6 / 12 was uniformly dispersed in PA66 in the resin region other than the polar interface region with the glass fiber.
[実施例5-7]
ガラスクロスの代わりに炭素繊維布帛を用いたこと以外は、実施例5-1と同様に連続繊維強化樹脂成形体を製造した。ガラス繊維との極界面領域以外の樹脂領域内では、PA6/12がPA66に均一に分散していた。[Example 5-7]
A continuous fiber reinforced resin molded body was produced in the same manner as in Example 5-1 except that the carbon fiber cloth was used instead of the glass cloth. PA6 / 12 was uniformly dispersed in PA66 in the resin region other than the polar interface region with the glass fiber.
[比較例5-1]
PA66のみを用いてフィルムを製造したこと以外は、実施例5-1と同様に連続繊維強化樹脂成形体を製造した。[Comparative Example 5-1]
A continuous fiber reinforced resin molded product was produced in the same manner as in Example 5-1 except that the film was produced using only PA66.
[比較例5-2]
PA6/12に代えてPA6T/6Iを用いたこと以外は、実施例5-1と同様に連続繊維強化樹脂成形体を製造した。ガラス繊維との極界面領域以外の樹脂領域内と極界面領域内のいずれでも、PA6T/6IがPA66に均一に分散していた。[Comparative Example 5-2]
A continuous fiber reinforced resin molded product was produced in the same manner as in Example 5-1 except that PA6T / 6I was used instead of PA6 / 12. PA6T / 6I was uniformly dispersed in PA66 in both the resin region other than the polar interface region with the glass fiber and the polar interface region.
[比較例5-3]
ガラスクロスを19.5cm×9.5cmに切り出し、純水で30質量%に調整したポリアミドエマルジョン(セポルジョンPA200、住友精化株式会社)の溶液に浸漬し、その後80℃の熱風循環乾燥機で1時間乾燥して複合材料を調製した。得られた複合材料の、ポリアミドエマルジョンの固形成分であるPA6/12のガラスクロスへの付着量は、6質量%であった。その後PA66のフィルムと積層し、実施例5-1と同様に連続繊維強化樹脂成形体を製造した。この例では、PA6/12が、PA66に均一に分散しておらず、極界面領域内にのみ存在していた。[Comparative Example 5-3]
A glass cloth was cut into 19.5 cm x 9.5 cm, immersed in a solution of a polyamide emulsion (Seporjon PA200, Sumitomo Seika Co., Ltd.) adjusted to 30% by mass with pure water, and then immersed in a hot air circulation dryer at 80 ° C. 1 The composite material was prepared by drying for hours. The amount of PA6 / 12, which is a solid component of the polyamide emulsion, attached to the glass cloth of the obtained composite material was 6% by mass. After that, it was laminated with a film of PA66 to produce a continuous fiber reinforced resin molded body in the same manner as in Example 5-1. In this example, PA6 / 12 was not uniformly dispersed in PA66 and was present only in the polar interface region.
[比較例5-4]
PA66とPA6/12を重量比1:8でドライブレンドした以外は、実施例5-1と同様に連続繊維強化樹脂成形体を製造した。ガラス繊維との極界面領域以外の樹脂領域内ではPA66がPA6/12に均一に分散していた。[Comparative Example 5-4]
A continuous fiber reinforced resin molded product was produced in the same manner as in Example 5-1 except that PA66 and PA6 / 12 were dry-blended at a weight ratio of 1: 8. PA66 was uniformly dispersed in PA6 / 12 in the resin region other than the polar interface region with the glass fiber.
実施例5-1~7、比較例5-1~4の結果を以下の表4に示す。
表4から、本実施形態の連続繊維強化樹脂成形体は、実施例5-1~7に示すように、該連続強化繊維の長さ方向に直交する断面における該連続強化繊維1本と該熱可塑性樹脂との間の極界面において、該連続強化繊維の周縁部から、該2種以上の連続強化繊維1本の半径の10分の1離れた周縁外側領域内では、該2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)以外の樹脂(副樹脂)の占有割合が、該主樹脂の占有割合よりも高いが、該周縁外側領域以外の樹脂領域内では、該2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)以外の各副樹脂が均一に分散しているか又は混合しているため、高い引張応力、曲げ応力、曲げ弾性率、高温での引張応力を示した。他方、比較例5-1に示すように、熱可塑性樹脂が1種類であると強化繊維と熱可塑性樹脂の接着が不十分となり、引張応力、曲げ応力、曲げ弾性率、高温での引張応力が低下した。また、比較例5-2、4に示すように、熱可塑性樹脂が2種類以上であっても、連続強化繊維の周縁部から、該2種以上の連続強化繊維1本の半径の10分の1離れた周縁外側領域内で、該2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)の占有割合が副樹脂の占有割合よりも高いと、強化繊維と熱可塑性樹脂の接着が不十分となり、引張応力、曲げ応力、曲げ弾性率、高温での引張応力が低下した。また、比較例3に示すように、連続強化繊維の周縁部から、該2種以上の連続強化繊維1本の半径の10分の1離れた周縁外側領域内に、該2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)以外の副樹脂が存在していたとしても、該周縁外側領域以外の樹脂領域内で、該副樹脂が均一に分散していないか又は混合していなかったため、高温での引張応力が低下した。 From Table 4, as shown in Examples 5-1 to 7, the continuous fiber reinforced resin molded body of the present embodiment has the continuous reinforcing fiber and the heat in a cross section orthogonal to the length direction of the continuous reinforcing fiber. At the polar interface with the plastic resin, the heat of the two or more kinds is within the outer peripheral region of the peripheral edge of the continuous reinforcing fiber, which is one tenth of the radius of one of the two or more kinds of continuous reinforcing fibers. Among the plastic resins, the occupancy ratio of the resin (secondary resin) other than the resin (main resin) having the highest occupancy ratio as a whole of the resin region is higher than the occupancy ratio of the main resin, but the resin other than the peripheral outer region. In the region, among the two or more types of thermoplastic resins, each sub-resin other than the resin (main resin) having the highest occupancy ratio as a whole in the resin region is uniformly dispersed or mixed, so that it is high. Tensile stress, bending stress, bending elasticity, and tensile stress at high temperature are shown. On the other hand, as shown in Comparative Example 5-1, if there is only one type of thermoplastic resin, the adhesion between the reinforcing fiber and the thermoplastic resin becomes insufficient, and tensile stress, bending stress, flexural modulus, and tensile stress at high temperature are increased. It has declined. Further, as shown in Comparative Examples 5-2 and 4, even if there are two or more types of thermoplastic resin, one tenth of the radius of one of the two or more types of continuous reinforcing fibers is provided from the peripheral edge of the continuous reinforcing fibers. Reinforced when the occupancy ratio of the resin (main resin) having the highest occupancy ratio as a whole of the resin region among the two or more types of thermoplastic resins is higher than the occupancy ratio of the secondary resin in the outer peripheral region 1 away. The adhesion between the fiber and the thermoplastic resin became insufficient, and the tensile stress, bending stress, bending elasticity, and tensile stress at high temperature decreased. Further, as shown in Comparative Example 3, the two or more types of thermoplasticity are contained in the peripheral outer region of the continuous reinforcing fiber, which is one tenth of the radius of one of the two or more types of continuous reinforcing fibers. Even if there is a secondary resin other than the resin (main resin) that occupies the highest proportion of the resin region as a whole, the secondary resin is uniformly dispersed in the resin region other than the peripheral outer region. The tensile stress at high temperature was reduced because it was not or was not mixed.
[実施例6-1]
ガラスクロス5枚とポリアミド樹脂のフィルム10枚を重ねてダブルベルトプレス装置により成形を行った。ポリアミド樹脂の吸水率は0.2wt%であった。得られた成形品の極界面領域の写真を図3に示す。[Example 6-1]
Five glass cloths and ten polyamide resin films were laminated and molded by a double belt press device. The water absorption rate of the polyamide resin was 0.2 wt%. A photograph of the polar interface region of the obtained molded product is shown in FIG.
[実施例6-2]
ガラスクロス5枚とポリアミド樹脂のフィルム10枚を重ねて金型による成形を行った。成形時間はポリアミド66の融点である265℃に達してから1分とし、金型を急冷した後に金型を開放し、成形体を取り出した。成形中の最大温度は285℃であった。ポリアミド樹脂の吸水率は0.2wt%であった。[Example 6-2]
Five glass cloths and ten polyamide resin films were laminated and molded by a mold. The molding time was set to 1 minute after reaching the melting point of 265 ° C. of the polyamide 66, the mold was rapidly cooled, the mold was opened, and the molded product was taken out. The maximum temperature during molding was 285 ° C. The water absorption rate of the polyamide resin was 0.2 wt%.
[実施例6-3]
ポリアミド樹脂のフィルムを成形前に真空乾燥機により乾燥させた以外は、実施例6-1と同様にして連続繊維強化樹脂複合材料を得た。ポリアミド樹脂の吸水率は0.01wt%であった。[Example 6-3]
A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 6-1 except that the polyamide resin film was dried by a vacuum dryer before molding. The water absorption rate of the polyamide resin was 0.01 wt%.
[実施例6-4]
ポリアミドフィルムと成形する際に、ポリアミド樹脂とカーボンブラックマスターバッチをドライブレンドして、成形しポリアミド樹脂フィルムとして使用した以外は、実施例1と同様にして連続繊維強化樹脂複合材料を得た。ポリアミド樹脂の吸水率は0.2wt%であった。カーボンブラックの含有量は90ppmであった。尚、実施例6-4以外の実施例、比較例では、粒子状添加材としてのカーボンブラックは含有されていない。[Example 6-4]
A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1 except that the polyamide resin and the carbon black masterbatch were dry-blended when molded into the polyamide film and used as the polyamide resin film. The water absorption rate of the polyamide resin was 0.2 wt%. The content of carbon black was 90 ppm. In Examples and Comparative Examples other than Example 6-4, carbon black as a particulate additive is not contained.
[実施例6-5]
ポリアミド66としてカルボキシル末端基の量が50μmol/g、カルボキシル末端基量が30μmol/gのものを使用した以外は、実施例6-1と同様にして連続繊維強化樹脂複合材料を得た。ポリアミド樹脂の吸水率は0.2wt%であった。
[Example 6-5]
A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 6-1 except that the polyamide 66 used had a carboxyl terminal group amount of 50 μmol / g and a carboxyl terminal group amount of 30 μmol / g. The water absorption rate of the polyamide resin was 0.2 wt%.
[実施例6-6]
ポリアミド66としてカルボキシル末端基の量が70μmol/g、アミノ末端基量が50μmol/gのものを使用した以外は、実施例6-1と同様にして連続繊維強化樹脂複合材料を得た。ポリアミド樹脂の吸水率は0.2wt%であった。[Example 6-6]
A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 6-1 except that the polyamide 66 used had a carboxyl terminal group amount of 70 μmol / g and an amino terminal group amount of 50 μmol / g. The water absorption rate of the polyamide resin was 0.2 wt%.
[実施例6-7]
ポリアミド66と、シランカップリング剤とカルボキシル末端基との反応を促進する触媒として次亜リン酸ナトリウム0.05wt%を二軸混錬機で混錬したものを、熱可塑性樹脂として使用した以外は、実施例6-1と同様にして連続繊維強化樹脂複合材料を得た。ポリアミド樹脂の吸水率は0.2wt%であった。[Example 6-7]
Except that 0.05 wt% of sodium hypophosphite was kneaded with a twin-screw kneader as a catalyst to promote the reaction between the polyamide 66, the silane coupling agent and the carboxyl end group, and used as a thermoplastic resin. , A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 6-1. The water absorption rate of the polyamide resin was 0.2 wt%.
[実施例6-8]
ガラス繊維の集束剤に次亜リン酸ナトリウムを0.05wt%添加したこと以外は、実施例6-1と同様にして連続繊維強化樹脂複合材料を得た。ポリアミド樹脂の吸水率は0.2wt%であった。[Example 6-8]
A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 6-1 except that 0.05 wt% of sodium hypophosphite was added to the glass fiber sizing agent. The water absorption rate of the polyamide resin was 0.2 wt%.
[実施例6-9]
金型として長辺方向が開口している金型を用いたこと以外は、実施例6-2と同様にして連続繊維強化樹脂複合材料を得た。ポリアミド樹脂の吸水率は0.2wt%であった。[Example 6-9]
A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 6-2, except that a mold having an opening in the long side direction was used as the mold. The water absorption rate of the polyamide resin was 0.2 wt%.
[比較例6-1]
集束剤を添加していないガラス繊維を用いたこと以外は、実施例1と同様にして連続繊維強化樹脂複合材料を得た。[Comparative Example 6-1]
A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 1 except that the glass fiber to which the sizing agent was not added was used.
[比較例6-2]
集束剤としてシランカップリング剤として3-グリシドキシプロピルトリメトキシシラン0.3質量%、エポキシ樹脂エマルジョン1.5質量%、カルナウバワックス0.2質量%を付着させたガラス繊維を用いたこと以外は、実施例6-1と同様にして連続繊維強化樹脂複合材料を得た。得られた成形品の極界面領域の写真を図4に示す。[Comparative Example 6-2]
As a sizing agent, a glass fiber to which 3-glycidoxypropyltrimethoxysilane 0.3% by mass, an epoxy resin emulsion 1.5% by mass, and carnauba wax 0.2% by mass was attached was used as a silane coupling agent. A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 6-1 except for the above. A photograph of the polar interface region of the obtained molded product is shown in FIG.
実施例6-3のように熱可塑性樹脂の吸水率が低いと、物性の低下がみられた。
実施例6-4のように粒子状添加材の含有量が高いと、物性の低下がみられた。
実施例6-5のようにポリアミド樹脂のカルボキシル末端基量が少ないと、物性の低下がみられた。
実施例6-6のようにポリアミド樹脂のアミノ末端基量が多いと、物性の低下がみられた。
実施例6-9のように熱可塑性樹脂の、プレス中の流動率が高いと、カップリング剤と熱可塑性樹脂に含まれている末端官能基が十分に反応せず、物性の低下がみられた。
集束剤を塗布していない連続強化繊維を用いた比較例6-1や、樹脂の末端基と反応性が実質的にないカップリング剤を含む集束剤を塗布した連続強化繊維を用いた比較例6-2では、引張応力、曲げ応力、曲げ弾性率が低下した。
When the water absorption rate of the thermoplastic resin was low as in Example 6-3, the physical properties were deteriorated.
When the content of the particulate additive was high as in Example 6-4, deterioration of physical properties was observed.
When the amount of the carboxyl-terminal group of the polyamide resin was small as in Examples 6-5, the physical properties were deteriorated.
When the amount of amino-terminal groups of the polyamide resin was large as in Examples 6-6, the physical properties were deteriorated.
When the flow rate of the thermoplastic resin in the press is high as in Examples 6-9, the coupling agent and the terminal functional groups contained in the thermoplastic resin do not sufficiently react with each other, and the physical properties are deteriorated. rice field.
Comparative Example 6-1 using a continuous reinforcing fiber to which a sizing agent was not applied, and a comparative example using a continuous reinforcing fiber to which a sizing agent containing a coupling agent having substantially no reactivity with the terminal group of the resin was applied. In 6-2, the tensile stress, bending stress, and flexural modulus decreased.
[実施例7-1]
ガラス繊維Aを用いたガラスクロス5枚とポリアミド樹脂Aのフィルム10枚を重ねて金型によりプレス成形を行った。成形時間はポリアミド66の融点である265℃に達してから1分とし、金型を急冷した後に金型を開放し、成形体を取り出した。成形中の最大温度は285℃であった。成形品のA/E法測定を行い、層間剥離起因の破壊強度を測定した。[Example 7-1]
Five glass cloths using the glass fiber A and ten films of the polyamide resin A were laminated and press-molded by a mold. The molding time was set to 1 minute after reaching the melting point of 265 ° C. of the polyamide 66, the mold was rapidly cooled, the mold was opened, and the molded product was taken out. The maximum temperature during molding was 285 ° C. The A / E method of the molded product was measured, and the fracture strength due to delamination was measured.
[実施例7-2]
連続強化繊維として、ガラス繊維Cを用いたこと以外は、実施例7-1と同様にして連続繊維強化樹脂複合材料を得た。[Example 7-2]
A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 7-1 except that glass fiber C was used as the continuous reinforcing fiber.
[実施例7-3]
ダブルベルト装置による成形を行ったこと以外は、実施例7-2と同様にして連続繊維強化樹脂複合材料を得た。[Example 7-3]
A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 7-2, except that molding was performed by a double belt device.
[比較例7-1]
ポリアミド66をガラスクロスに含浸したBond Laminate製「Tepex dynalite 101」に関して、実施例7-1と同様の評価を行った。[Comparative Example 7-1]
The same evaluation as in Example 7-1 was performed on "Tepex dynarite 101" manufactured by Bond Laminate in which polyamide 66 was impregnated into a glass cloth.
上記表6から、実施例7-1~3の連続繊維強化樹脂複合材料は、比較例7-1に比べて、層間剥離起因の破壊強度が高いため、非常に高い引張応力、曲げ応力、曲げ弾性率、衝撃特性を示した。 From Table 6 above, the continuous fiber reinforced resin composite materials of Examples 7-1 to 3 have higher fracture strength due to delamination as compared with Comparative Example 7-1, and therefore have extremely high tensile stress, bending stress, and bending. The elastic modulus and impact characteristics were shown.
[実施例8-1]
ガラス繊維Aを用いたガラスクロス5枚とポリアミド樹脂Aのフィルム10枚を重ねて金型によりプレス成形を行った。成形時間はポリアミド66の融点である265℃に達してから1分とし、金型を急冷した後に金型を開放し、成形体を取り出した。成形中の最大温度は285℃であった。ガラス繊維Aとポリアミド樹脂Aとのμドロップ生成係数は25であった。[Example 8-1]
Five glass cloths using the glass fiber A and ten films of the polyamide resin A were laminated and press-molded by a mold. The molding time was set to 1 minute after reaching the melting point of 265 ° C. of the polyamide 66, the mold was rapidly cooled, the mold was opened, and the molded product was taken out. The maximum temperature during molding was 285 ° C. The μ drop formation coefficient of the glass fiber A and the polyamide resin A was 25.
[実施例8-2]
ガラス繊維Cを用いたこと以外は、実施例8-1と同様にして連続繊維強化樹脂複合材料を得た。ガラス繊維Cとポリアミド樹脂Aとのμドロップ生成係数は27であった。[Example 8-2]
A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 8-1 except that the glass fiber C was used. The μ drop formation coefficient of the glass fiber C and the polyamide resin A was 27.
[比較例8-1]
ポリアミド樹脂としてポリアミド樹脂Cのフィルムを使用したこと以外は実施例8-1と同様にして連続繊維強化樹脂複合材料を得た。ガラス繊維Aとポリアミド樹脂Cとのμドロップ生成係数は3であった。[Comparative Example 8-1]
A continuous fiber reinforced resin composite material was obtained in the same manner as in Example 8-1 except that the film of polyamide resin C was used as the polyamide resin. The μ drop formation coefficient of the glass fiber A and the polyamide resin C was 3.
[比較例8-2]
ガラス繊維としてガラス繊維Cを用いたこと以外は、比較例8-1と同様にして連続繊維強化樹脂複合材料を得た。ガラス繊維Cとポリアミド樹脂Cとのμドロップ生成係数は3であった。[Comparative Example 8-2]
A continuous fiber reinforced resin composite material was obtained in the same manner as in Comparative Example 8-1 except that glass fiber C was used as the glass fiber. The μ drop formation coefficient of the glass fiber C and the polyamide resin C was 3.
上記表7から、実施例8-1~2の連続繊維強化樹脂複合材料は、、比較例8-1~2に比べて、μドロップ生成係数が高いため、非常に高い引張応力、曲げ応力、曲げ弾性率、衝撃特性、長期特性を示した。 From Table 7 above, the continuous fiber reinforced resin composite materials of Examples 8-1 and 8 have a higher μ drop generation coefficient than those of Comparative Examples 8-1 and 8, so that the tensile stress and bending stress are very high. The flexural modulus, impact characteristics, and long-term characteristics were shown.
[実施例9]
図12に示す形状のスマートフォン筐体を作製した。ガラス繊維Cを用いたガラスクロス1枚をポリアミド樹脂Aのフィルムで挟み、プレス成形を行った。
得られた成形品は、製品肉厚0.4mmであり、寸法が長手方向135mm、幅方向65mm、側壁の高さ5mmであり、長手方向の引張強度が550MPa、曲げ弾性率が35MPa、幅方向の引張強度が530MPa、曲げ弾性率が33MPaであった。また、成形品の平面部の電界シールド特性をKEC法によって測定した結果、周波数1GHz帯において、0dBと電波透過性に優れた物であった。
成形品の外観は、繊維乱れのない外観良好な成形品であった。
上記引張強度は、JIS K7161に準拠して測定した。また、上記曲げ弾性率は、JIS K7171に準拠して測定した。また、上記電界シールド特性は、5cm×5cmの正方形に切り取った成形品をアルミ製のサンプル固定治具に導電性テープで貼りつけ、「Anritsu」製電波シールド特性試験器MA8602Cを用いて電解をかけ(KEC法)、1GHzにおける電解シールド特性を「Anritsu」製スペクトルアナライザーMS2661Cを用いて測定した。[Example 9]
A smartphone housing having the shape shown in FIG. 12 was produced. A piece of glass cloth using glass fiber C was sandwiched between films of polyamide resin A and press-molded.
The obtained molded product has a product wall thickness of 0.4 mm, dimensions of 135 mm in the longitudinal direction, 65 mm in the width direction, and a height of the side wall of 5 mm, a tensile strength in the longitudinal direction of 550 MPa, a flexural modulus of 35 MPa, and a flexural modulus in the width direction. The tensile strength was 530 MPa and the flexural modulus was 33 MPa. Further, as a result of measuring the electric field shielding characteristic of the flat surface portion of the molded product by the KEC method, it was found to be excellent in radio wave transmission at 0 dB in the frequency 1 GHz band.
The appearance of the molded product was a good appearance without fiber disorder.
The tensile strength was measured according to JIS K7161. The flexural modulus was measured according to JIS K7171. For the electric field shield characteristics, a molded product cut into a 5 cm x 5 cm square is attached to an aluminum sample fixing jig with conductive tape, and electrolyzed using the radio shield characteristic tester MA8602C manufactured by "Anritsu". (KEC method) The electrolytic shield characteristics at 1 GHz were measured using a spectrum analyzer MS2661C manufactured by "Anritsu".
[実施例10]
ガラス繊維Cを3mmにチョップ加工したものを、同方向回転二軸混練押出機HK-25D(41D)Φ25mm、L/D=41(株式会社パーカーコーポレーション)と計量装置(重量式二軸スクリューフィーダーK-CL-24-KT20(K-トロン社))を用いて、スクリュ回転数175rpm、供給量5kg/hで、ポリアミド樹脂Aと混練し、ペレットを得た。得られたペレットを用いて、電動式射出成形機(NEX140(日精樹脂工業株式会社)、型締め力140tf/スクリュ径Φ40/フルフライトスクリュ)を用いて、JIS K 7152-1に準拠した条件で、JIS K 7139多目的試験片タイプA1、t4mm成形品を作成した。この時の極界面部の観察写真を図10に示す。[Example 10]
Glass fiber C chopped to 3 mm, same-direction rotating twin-screw kneading extruder HK-25D (41D) Φ25 mm, L / D = 41 (Parker Corporation) and weighing device (heavy-duty twin-screw feeder K) -CL-24-KT20 (K-Tron)) was kneaded with the polyamide resin A at a screw rotation speed of 175 rpm and a supply amount of 5 kg / h to obtain pellets. Using the obtained pellets, an electric injection molding machine (NEX140 (Nissei Resin Industry Co., Ltd.), mold clamping force 140tf / screw diameter Φ40 / full flight screw) was used under the conditions compliant with JIS K7152-1. , JIS K 7139 Multipurpose test piece type A1, t4 mm molded product was prepared. An observation photograph of the polar interface at this time is shown in FIG.
[比較例10]
ポリアミド樹脂をポリアミド樹脂Cとしたこと以外は、実施例10と同様にして成形品を作成した。この時の極界面部の観察写真を図11に示す。
図10、11に示すように、μドロップ生成係数が10以上であり、ガラス繊維と樹脂との相性が良いものでは、良好な極界面を形成することができる。[Comparative Example 10]
A molded product was produced in the same manner as in Example 10 except that the polyamide resin was the polyamide resin C. An observation photograph of the polar interface at this time is shown in FIG.
As shown in FIGS. 10 and 11, if the μ drop generation coefficient is 10 or more and the compatibility between the glass fiber and the resin is good, a good polar interface can be formed.
本実施形態の連続繊維強化樹脂成形体は、各種機械や自動車等の構造部品等、高レベルでの機械的物性が要求される材料の補強材として、また、熱可塑性樹脂組成物との複合成形体材料として、産業上の利用可能である。また、本発明に係る連続繊維強化樹脂複合材料の製造方法により、連続強化繊維と熱可塑性樹脂との間の極界面における接着力、親和性が高く、該極界面に存在する空隙が少なく、十分な強度を発現する連続繊維強化樹脂複合材料を得ることができる。 The continuous fiber reinforced resin molded body of the present embodiment is used as a reinforcing material for materials that require high-level mechanical properties such as structural parts of various machines and automobiles, and is composite molded with a thermoplastic resin composition. It can be used industrially as a body material. Further, according to the method for producing a continuous fiber reinforced resin composite material according to the present invention, the adhesive strength and affinity at the polar interface between the continuous reinforced fiber and the thermoplastic resin are high, and there are few voids existing at the polar interface, which is sufficient. It is possible to obtain a continuous fiber reinforced resin composite material that exhibits high strength.
r 略丸断面の連続強化繊維の半径
1 合成樹脂
2 連続強化繊維
3 空隙
4 連続強化繊維束
5 連続強化繊維の長さ方向に直交する断面における該連続強化繊維1本と該熱可塑性樹脂との間の極界面において、該連続強化繊維の周縁部から、該連続強化繊維1本の半径の10分の1離れた周縁外側領域
6 連続強化繊維
7 2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)以外の樹脂(副樹脂)
8 2種以上の熱可塑性樹脂の内、樹脂領域の全体として占有割合が最も高い樹脂(主樹脂)r Radius of continuous reinforcing fiber with substantially round cross section 1
8 Of the two or more types of thermoplastic resins, the resin (main resin) that occupies the highest proportion of the entire resin region.
Claims (14)
バンドソーにより1cm角に切削した連続繊維強化樹脂成形体の連続強化繊維の長さ方向に直交する断面を、研磨面に400g/cm2の力がかかるように、研磨台を100rpmで回転させて、耐水ペーパー番手#220で10分間、耐水ペーパー番手#400で2分間、耐水ペーパー番手#800で5分間、耐水ペーパー番手#1200で10分間、耐水ペーパー番手#2000で15分間、炭化ケイ素フィルム粒度9μmで15分間、アルミナフィルム粒度5μmで15分間、アルミナフィルム粒度3μmで15分間、アルミナフィルム粒度1μmで15分間、バフ研磨紙発泡ポリウレタンを用いた粒度0.1μmのコロイダルシリカで10分間の順番で、各研磨で7mL/minで水を加えながら研磨し、研磨したサンプルを、走査型電子顕微鏡(SEM)で観察し画像解析することで、空隙率を下記式:
空隙率(%)=(連続強化繊維の周縁部から該連続強化繊維の半径の10分の1離れた周縁外側領域内の空隙の面積)/(連続強化繊維の周縁部から該連続強化繊維の半径の10分の1離れた周縁外側領域の面積)×100
により求める。 A continuous fiber reinforced resin molded body composed of a continuously reinforced fiber having a substantially round cross section and a thermoplastic resin, and between the one continuous reinforced fiber and the thermoplastic resin in a cross section orthogonal to the length direction of the continuous reinforced fiber. At the polar interface of the continuous reinforcing fiber, the void ratio obtained by the following method in the peripheral outer peripheral region separated from the peripheral edge portion of the continuous reinforcing fiber by 1/10 of the radius of one continuous reinforcing fiber is 10% or less. A continuous fiber reinforced resin molded body characterized in that the number of reinforcing fibers is 10% or more of the total number of continuous reinforcing fibers.
The polishing table is rotated at 100 rpm so that a force of 400 g / cm 2 is applied to the polished surface of the cross section of the continuous fiber reinforced resin molded body cut into 1 cm squares with a band saw . Water resistant paper count # 220 for 10 minutes, water resistant paper count # 400 for 2 minutes, water resistant paper count # 800 for 5 minutes, water resistant paper count # 1200 for 10 minutes, water resistant paper count # 2000 for 15 minutes, silicon carbide film Alumina film grain size of 5 μm for 15 minutes, Alumina film grain size of 3 μm for 15 minutes, Alumina film grain size of 1 μm for 15 minutes, and colloidal silica with a grain size of 0.1 μm using buffed abrasive paper foamed polyurethane for 10 minutes. In order, each polishing was polished while adding water at 7 mL / min, and the polished sample was observed with a scanning electron microscope (SEM) and image -analyzed to determine the void ratio by the following formula:
Porosity (%) = (Area of voids in the peripheral outer region of the continuous reinforcing fiber 1/10 of the radius of the continuous reinforcing fiber) / (From the peripheral edge of the continuous reinforcing fiber to the continuous reinforcing fiber Area of outer peripheral area 1/10 of radius away) x 100
Obtained by.
カップリング剤、結束剤、及び潤滑剤からなる集束剤が添加されている連続強化繊維と、該カップリング剤と反応性がある末端官能基を有する熱可塑性樹脂とを、該熱可塑性樹脂の融点以上となるように加熱プレスする工程;及び
これを該熱可塑性樹脂の融点以下まで冷却し、成形品として連続繊維強化樹脂成形体を得る工程;
を含む、請求項1に記載の連続繊維強化樹脂成形体の製造方法。 The following steps:
The melting point of the thermoplastic resin is a continuous reinforcing fiber to which a sizing agent consisting of a coupling agent, a sizing agent, and a lubricant is added, and a thermoplastic resin having a terminal functional group reactive with the coupling agent. The step of heat-pressing so as to be as described above; and the step of cooling this to below the melting point of the thermoplastic resin to obtain a continuous fiber reinforced resin molded product as a molded product;
The method for producing a continuous fiber reinforced resin molded product according to claim 1.
長手方向の引張強度(MPa)×0.5+幅方向の引張強度(MPa)×0.5>500MPa 式(3)
の関係を満たし、曲げ弾性率が、下記式(4):
長手方向の曲げ弾性率(MPa)×0.5+幅方向曲げ弾性率(MPa)×0.5>30MPa 式(4)
の関係を満たし、かつ、KEC法により測定される電界シールド性が、周波数1GHz帯において、10dB以下であることを特徴とする、通信機器筐体。 A communication device housing made of a continuous fiber reinforced resin molded body made of the thermoplastic resin according to claim 1 and continuous glass reinforced fibers, wherein the tensile strength is the following formula (3) :.
Longitudinal tensile strength (MPa) x 0.5 + Width tensile strength (MPa) x 0.5> 500 MPa Formula (3)
Satisfying the relationship of, the flexural modulus is the following equation (4):
Longitudinal flexural modulus (MPa) x 0.5 + Width flexural modulus (MPa) x 0.5> 30 MPa Formula (4)
A communication device housing characterized in that the electric field shielding property measured by the KEC method is 10 dB or less in a frequency band of 1 GHz.
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